JP2013025093A - Method for producing electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic toner compatibly achieving favorable low-temperature fixability and a charging property under high-temperature and high-humidity environment and having an excellent heat-resistant storage property, and a method for producing the same.SOLUTION: The method for producing electrophotographic toner including the following steps (1)-(3) and the electrophotographic toner obtained by the method are provided. The method includes the step (1): for, after and/or while adjusting pH of aqueous liquid mixture containing agglomerated particles which contains resin particles (A) and mold releasing agent particles, and a surfactant under a temperature of 25°C to 2.0 to 5.0, fusing the agglomerated particles in the aqueous liquid mixture; the step (2) for adjusting pH of the fused particle dispersed liquid that has been obtained in the step (1) under a temperature of 25°C to 5.5 to 7.5; and (3): for filtering a liquid component from the fused particle dispersed liquid that has been obtained in the step (2) to obtain toner particles.

Description

  The present invention relates to a method for producing an electrophotographic toner and an electrophotographic toner obtained thereby.

In the field of electrophotographic toner, with development of an electrophotographic system, development of a toner corresponding to high image quality and high speed is required.
As a method for controlling the particle size and reducing the particle size in response to higher image quality, an aggregation 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 an amorphous polyester and a crystalline polyester having 2.0 to 12.0 mol% of a structural unit derived from a trivalent or higher carboxylic acid for the purpose of improving low-temperature fixability and hot offset resistance. A step of emulsifying the raw material polyester contained in an aqueous medium, or after mixing the raw material polyester with an organic solvent, an aqueous medium is added and emulsified to obtain a polyester particle dispersion, and the polyester particle dispersion is agglomerated and An electrophotographic toner obtained by unity is disclosed.
Patent Document 4 discloses a dispersion of toner particles including core particles formed by agglomerating resin particles, pigment particles, and wax particles for the purpose of prolonging the life and preventing omission and scattering during transfer. A step of reslurry washing with an alkaline solution of pH 8-12, a step of reslurry washing of the toner particle dispersion with an acidic solution of pH 2-6, a step of reslurry washing with the alkaline solution, A method for producing a toner is disclosed which includes a penetrating water cleaning process using an acidic solution and a penetrating water cleaning process using an alkaline solution between the steps of performing a reslurry cleaning process using an acidic solution.
In Patent Document 5, for the purpose of improving the chargeability of the toner and efficiently removing the discharge products adhering to the surface of the image holding member, In order to obtain an electrostatic charge image developing toner in which the amount of Na ions on the surface of the particle size side toner is in a specific range, the step of washing the toner with a treatment liquid having a pH of 9 or more and pH 10 or less, and the toner was adjusted to a pH of 4 or less. Thereafter, it is disclosed that the cleaning is performed by a cleaning process including a process of cleaning while treating with ultrasonic waves and a process of cleaning the toner with ion-exchanged water.
In Patent Document 6, for the purpose of improving storage stability and developability, a step of obtaining a dispersion of toner particles containing polyester in an aqueous medium in the presence of a surfactant, and the obtained toner particles There is disclosed a method for producing an electrophotographic toner having a step of washing with an aqueous alcohol solution containing 0.1 to 5% by weight of an alcohol having a number of 1 to 5.

JP 2009-75342 A JP 2009-122694 A International Publication No. 2010/27071 Pamphlet JP 2010-113112 A JP 2010-78993 A JP 2010-39102 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 low heat storage stability, which is stability at high temperature storage, and low chargeability.
An object of the present invention is to provide an electrophotographic toner that has both good low-temperature fixability and chargeability under high temperature and high humidity, and excellent heat-resistant storage stability, and a method for producing the same.

  The inventors of the present invention have considered that the factors affecting the fixing temperature, chargeability, and heat-resistant storage stability are the position 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 and the surfactant are fused, and the agglomerated particles in the aqueous mixture having a specific pH are fused and adjusted to a specific pH, and then the liquid portion It has been found that an electrophotographic toner having both good low-temperature fixability and chargeability under high temperature and high humidity and excellent heat-resistant storage stability can be obtained by removing.

That is, the present invention provides the following [1] and [2].
[1] A method for producing an electrophotographic toner comprising the following steps (1) to (3).
Step (1): After adjusting the pH at 25 ° C. of the aqueous mixed solution containing the aggregated particles including the resin particles (A) and the release agent particles and the surfactant to 2.0 to 5.0 and / or Or a step of fusing the aggregated particles in the aqueous mixed solution while adjusting,
Step (2): Step of adjusting the pH of the fused particle dispersion obtained in Step (1) at 25 ° C. to 5.5 to 7.5 Step (3): Fusion obtained in Step (2) Step of removing liquid part from particle dispersion to obtain toner particles [2] An electrophotographic toner obtained by the production method described in [1] above.

  According to the present invention, it is possible to provide an electrophotographic toner that has both good low-temperature fixability and chargeability under high temperature and high humidity, and excellent heat resistant storage stability, and a method for producing the same.

The method for producing an electrophotographic toner of the present invention includes the following steps (1) to (3).
Step (1): After adjusting the pH at 25 ° C. of the aqueous mixed solution containing the aggregated particles including the resin particles (A) and the release agent particles and the surfactant to 2.0 to 5.0 and / or Or a step of fusing the aggregated particles in the aqueous mixed solution while adjusting,
Step (2): Step of adjusting the pH of the fused particle dispersion obtained in Step (1) at 25 ° C. to 5.5 to 7.5 Step (3): Fusion obtained in Step (2) Step of removing toner from particle dispersion to obtain toner particles

The reason why the electrophotographic toner obtained by the production method of the present invention has both good low-temperature fixability and high-temperature high-humidity chargeability and excellent heat-resistant storage stability is not clear, but is as follows. Can be considered.
In the step (1) of 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 (25 ° C.) of the aqueous mixed solution containing the aggregated particles is It is adjusted to 2.0 to 5.0. When fusion is performed at a pH in this range, that is, acidic, the dispersibility of the resin particles becomes unstable, and fusion occurs quickly. Therefore, the fusion is completed before the release agent dissolves or separates. Therefore, even if the release agent is added to the extent that it has an effect on low-temperature fixability, the release agent is exposed to the toner surface. Is suppressed, and the chargeability is considered to be good.
On the other hand, it is considered that the inclusion of a surfactant localizes the surface of the aggregated particles, prevents fusion of the aggregated particles, and provides a toner having a sharp particle size distribution.
Furthermore, in step (2) of the present invention, the pH at 25 ° C. of the fused particle dispersion obtained in step (1) is adjusted to 5.5 to 7.5, and in step (3), the liquid portion is filtered. Separately, toner particles are obtained. The resin in the resin particles is sufficiently removed from the surface of the toner by sufficiently solidifying the liquid property of the dispersion by changing the liquidity of the dispersion to a pH in this range, that is, neutral to weakly acidic, and separating the solid and liquid. It is considered that the chargeability, particularly the chargeability under high temperature and high humidity, and the heat resistant storage stability can be compatible.
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) improves the low-temperature fixability of the toner and prevents hot offset. In the resin constituting the resin particles (A), 1 to 50% by weight is preferable, 10 to 50% by weight is preferable, 10 to 30% by weight is further preferable, and 13 to 20% by weight is particularly preferable.

(Crystalline polyester (a))
In the present invention, the crystalline polyester (a) is the 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 in (1) is from 0.6 to 1.4, and from the viewpoint of low-temperature fixability of the toner, 0.8 to 1.3 is preferable, and 0.9 to 1.2. More preferably, the thing of 0.9-1.1 is still more preferable.
The crystalline polyester (a) preferably has an acid group at the molecular end from the viewpoint of dispersion stability and emulsification of the resin particle dispersion (A). Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphonic acid group, and a sulfinic acid. Among these, a carboxyl group is preferable from the viewpoint of achieving both the dispersibility of the resin and the storage stability of the obtained toner.

The melting point of the crystalline polyester (a) is preferably from 50 to 150 ° C., more preferably from 55 to 130 ° C., and further preferably from 60 to 90 ° C., from the viewpoints of low-temperature fixability, chargeability, scattering suppression, and heat-resistant storage stability of the toner. 60-60 degreeC is preferable and especially 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 particularly preferably 60 to 85 ° C.
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 more preferably 3,000 to 5,000, from the viewpoints of low-temperature fixability and heat-resistant storage stability of the toner. 5,000 is more preferable.
The acid value of the crystalline polyester (a) is preferably from 5 to 30 mgKOH / g, more preferably from 10 to 27 mgKOH / g, from the viewpoint of dispersion stability and charge amount of the resin particle dispersion (A) of the toner. 25 mgKOH / g is more preferable, 15-25 mgKOH / g is still more preferable, and 15-22 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 and number average molecular weight 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 weight 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 using the mixture mixed by the ratio which uses all the crystalline polyester (a).

The crystalline polyester (a) can be produced by polycondensation reaction of an acid component and an alcohol component, preferably in the presence of a catalyst, preferably at 180 to 250 ° C.
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 (C1 to C3) esters. Of these, aliphatic dicarboxylic acids are preferred from the viewpoint of low-temperature fixability, heat-resistant storage stability and chargeability of the toner.
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, and the like. Among them, sebacic acid and 1,12-dodecanedioic acid are preferable from the viewpoints of low-temperature fixability, heat-resistant storage stability and chargeability of the toner.
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 alkanediol is preferable from the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner. Those of ˜12 are more preferred.
Specific examples of α, ω-linear alkanediol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane. Examples include diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like. From the viewpoints of storage stability and chargeability, 1,6-hexanediol and 1,9-nonanediol are preferred.
Specific examples of other aliphatic diols having 2 to 12 carbon atoms in the main chain include neopentyl glycol and 1,4-butenediol.
Specific examples of the aromatic diol include alkylene (carbon) of bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane. Number 2-3) Oxide adduct (average number of added moles 1-16) and the like.
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 the catalyst, from the viewpoint of the efficiency of the condensation polymerization reaction, a tin compound, a titanium compound, and the like are preferable, a tin compound is more preferable, and di (2-ethylhexanoic acid) tin, dibutyltin oxide, and the like can be given.
Examples of the titanium compound include titanium diisopropylate bistriethanolamate.
Although there is no restriction | limiting in the usage-amount of a catalyst, 0.01-1 weight part is preferable with respect to 100 weight part of total amounts of an acid component and an alcohol component, and 0.1-0.6 weight part is more preferable.

  The polycondensation reaction is preferably performed by adding an acid component and an alcohol component to a reaction vessel and maintaining at 140 to 200 ° C. for 5 to 15 hours, and then adding a catalyst and maintaining at 140 to 200 ° C. for 1 to 5 hours. Then, the reaction is allowed to proceed, and the method of obtaining the crystalline polyester by reducing the pressure to 5.0 to 20 kPa and maintaining it for 1 to 10 hours is preferable.

(Amorphous polyester (c))
The resin particles (A) preferably further contain an amorphous polyester (c) from the viewpoints of improving the heat-resistant storage stability and chargeability while maintaining the low-temperature fixability of the toner and preventing hot offset. 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. % By weight, more preferably 80 to 100% by weight, still more preferably 90 to 100% by weight, and particularly preferably substantially 100% by weight. The weight ratio ((a) / (c)) of the crystalline polyester (a) to the amorphous polyester (c) in the resin particles (A) improves the low-temperature fixability, heat-resistant storage stability and chargeability of the toner. From the viewpoint of preventing hot offset, 5/95 to 50/50 is preferable, 5/95 to 40/60 is more preferable, 10/90 to 30/70 is more preferable, and 13/87 to 25/75. Is more preferable, and 15/85 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. However, it is preferable to use a resin having the same composition from the viewpoints of aggregation control and low-temperature fixability of the toner.

The amorphous polyester (c) can be produced by polycondensation reaction between an acid component and an alcohol component, and preferred acid components and alcohol components are the same as those for the amorphous polyester (b). More than one species may be used. Specifically, preferred acid components include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, and acid anhydrides and alkyl (C1 to C3) esters thereof. Among them, dicarboxylic acid is preferable.
The dicarboxylic acid is preferably an aromatic dicarboxylic 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.
As the aromatic dicarboxylic acid, terephthalic acid is preferable, and as a specific example 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 is preferable, and trivalent or more. As the polyvalent carboxylic acid, trimellitic acid and its acid anhydride are preferable.

Preferred alcohol components include aromatic diols such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane. An alkylene (2 to 3 carbon atoms) oxide adduct (average number of added moles 1 to 16) is preferred.
The glass transition point, 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 contains two types of polyesters having different softening points from the viewpoint of low-temperature fixability, offset resistance and durability of the toner. It is preferable to do. 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 weight 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 release agent and 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.

In addition, the resin particles (A) may be particles composed only of a resin or may be colorant-containing resin particles containing a colorant. From the viewpoint of sharpening the particle size distribution of the toner, the colorant It is preferable that it is a coloring agent containing resin particle containing a coloring agent.
When the resin particles (A) are colorant-containing resin particles, the content of the colorant is 1 to 20 weights with respect to 100 parts by weight of the resin constituting the resin particles (A) from the viewpoint of toner image density. Part is preferable, and 5 to 10 parts by weight is more preferable.

(Coloring agent)
The colorant used in the present invention may be used as a colorant particle in an aqueous medium by surface treatment or use of a dispersant, or may be used by being contained in resin particles such as resin particles (A). From the viewpoint of sharpening the particle size distribution of the toner, the resin particles (A) are preferably used.
As the colorant, pigments and dyes are used, and pigments are preferable from the viewpoint of 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 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, but the alkaline aqueous solution and the optional components may be used. 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 low-temperature fixability of the toner.
In mixing, it is preferable to add a surfactant from the viewpoint of the emulsion stability 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 ammonia. From the viewpoint of improving the dispersibility of the resin, potassium hydroxide and sodium hydroxide are preferable. . Moreover, 1-30 weight% is preferable, as for the density | concentration of the alkali in aqueous alkali solution, 1-25 weight% is more preferable, and 1.5-20 weight% is still more preferable.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, etc. Among them, nonionic surfactants are preferable, and nonionic surfactants and anionic surfactants or It is more preferable to use 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 weight ratio of the nonionic surfactant to the anionic surfactant (nonionic surfactant / anionic surfactant) is sufficient for the resin. From the viewpoint of emulsifying, it is preferably 0.3 to 10, and more preferably 0.5 to 5.

Nonionic surfactants include polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, oxyethylene / oxypropylene block copolymers, and the like. From the viewpoint, polyoxyethylene alkyl ethers are preferable.
Examples of polyoxyethylene alkylaryl ethers include polyoxyethylene nonylphenyl ether.
Examples of polyoxyethylene alkyl ethers include polyoxyethylene oleyl ether and polyoxyethylene lauryl ether.
Examples of polyoxyethylene fatty acid esters include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, and the like.

Specific examples of the anionic surfactant include dodecyl benzene sulfonic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium alkyl ether sulfate, etc., among them, from the viewpoint of emulsion stability of the resin, dodecyl benzene sulfonic acid. Sodium and sodium alkyl ether sulfates 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 weight or less, more preferably 15 parts by weight or less, still more preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the resin constituting the resin particles (A). 0.5-10 weight part 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 point, and the homogeneous resin particles are obtained. 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).
The aqueous medium preferably contains water as a main component, and from the viewpoint of environmental properties, the water content in the aqueous medium is preferably 80% by weight or more, more preferably 90% by weight or more, and further 95% by weight or more. Preferably, substantially 100% by weight is 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 aliphatic alcohols having 1 to 5 carbon atoms; dialkyl (carbon numbers 1 to 3) ketones such as acetone and methyl ethyl ketone; and cyclic ethers such as tetrahydrofuran are used. Among these, from the viewpoint of preventing mixing into the toner, an aliphatic 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 point 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 weight / 100 parts by weight 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 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 more preferable. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

  The amount of the aqueous medium used is preferably 100 to 2000 parts by weight, and 150 to 1500 parts by weight with respect to 100 parts by weight of the resin constituting the resin particles (A) from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. More preferred is 150 to 500 parts by weight. From the viewpoint of the stability and ease of handling of the obtained resin particle dispersion, the solid content concentration is preferably 7 to 50% by weight, more preferably 10 to 40% by weight, still more preferably 20 to 40% by weight, More preferably, it is 25 to 35% by weight. 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 toner capable of obtaining a high-quality image, 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 size is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles is preferably 40% or less, more preferably 35% or less, and more preferably 30% from the viewpoint of obtaining a toner capable of obtaining a high-quality image. The following is more preferable, and 28% or less is 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 average particle size (μm)] × 100

[Releasing agent particles]
The release agent particles preferably contain a surfactant from the viewpoint of aggregation. In the case of using the surfactant, the content is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the release agent, and preferably 0.1 to 5 parts from the viewpoint of aggregation properties and chargeability of the obtained toner. Part by weight is more preferred.
The volume median particle size of the release agent particles is preferably 0.1 to 1 μm, more preferably 0.1 to 0.7 μm, and more preferably 0.1 to 0.7 μm from the viewpoint of preventing chargeability and hot offset of the obtained toner. 5 μm is more preferable.
The CV value of the release agent particles is preferably 15 to 50%, more preferably 15 to 40%, and still more preferably 15 to 35%, from the viewpoint of the chargeability of the obtained toner.

(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., further preferably 75 to 90 ° C., and more preferably 80 to 90 ° C. from the viewpoints of low-temperature fixability, heat-resistant storage stability and chargeability of the toner. ° C is even more preferred.
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 weight 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 usually preferably 1 to 20 parts by weight with respect to 100 parts by weight of the resin in the toner from the viewpoint of improving the low-temperature fixability by improving the releasability of the toner and from the viewpoint of chargeability. 2 to 15 parts by weight 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.
As the aqueous medium and the surfactant used in the production, those used for obtaining the resin mixture are preferably used.

[Surfactant used in step (1)]
In step (1) of the present invention, a surfactant is used.
Examples of the surfactant used in the step (1) include nonionic surfactants, anionic surfactants, and cationic surfactants. Among them, the fusion between the aggregated particles is effectively prevented, From the viewpoint of obtaining a toner having a sharp diameter distribution, a nonionic surfactant and an anionic surfactant are preferable, and an anionic surfactant is more preferable.

As the anionic surfactant, an anionic surfactant having a polyethylene glycol moiety having an average added mole number of ethylene oxide of 5 to 100 is preferable. The average added mole number of the ethylene oxide is 5 to 100 mol from the viewpoint of improving the stability of the aggregated particles and the fusing property of the resin particles, and improving the charging property, scattering property and heat-preserving property of the obtained toner. Is preferable, 6-50 mol is more preferable, 9-30 mol is more preferable, 11-20 mol is still more preferable, and 12-15 mol is still more preferable.
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.
Preferable anionic surfactants include sulfate ester salts and sulfonate salts having an average addition mole number of ethylene oxide of 5 to 100, and sulfate ester salts are preferred.

  The sulfate ester salt is preferably a sulfate ester salt represented by the following general formula (1), polyoxyethylene alkyl ether sulfate, polyoxyethylene polyoxypropylene alkyl ether sulfate or the like, represented by the following general formula (1). Sulfuric acid ester salts and polyoxyethylene alkyl ether sulfates are more preferable, and sulfuric acid ester salts represented by the following general formula (1) are more preferable.

（式中、Ｒ¹は、水素原子又は炭素数１〜１２のアルキル基を表し、Ｒ²は、水素原子又はメチル基を表し、ｍは平均値が１〜４であり、ＡＯはエチレンオキシ基及び／又はプロピレンオキシ基を表し、ｎは平均値が５〜１００であり、Ｍはアンモニウム、テトラアルキルアンモニウム、アルカリ金属を表す。）

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a methyl group, m represents an average value of 1 to 4, and AO represents an ethyleneoxy group. And / or represents a propyleneoxy group, n has an average value of 5 to 100, and M represents ammonium, tetraalkylammonium, or an alkali metal.)

R ¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms from the viewpoint of improving the charging property, scattering property and heat-resistant storage stability of the toner. An atom or a methyl group is more preferable, and a hydrogen atom is still more preferable.

R ² represents a hydrogen atom or a methyl group from the viewpoint of improving the stability of the agglomerated particles and the fusing property of the resin particles, and improving the charging property, scattering property and heat-preserving property of the resulting toner. Is preferred. The plurality of R ² may be the same or different, but are preferably the same.
The sulfate ester salt represented by the general formula (1) may be a mixture of compounds in which m is any one of 1 to 4, and m has an average value of 1 to 4, and the chargeability of the toner. From the viewpoint of improving scatterability and heat-resistant storage stability, 2 to 3 is preferable and 2 is more preferable.
In the case where R ² is a hydrogen atom, the average value of m is preferably 2 to 3, and more preferably 3.
The average value of m when R ² is a methyl group is preferably 1 to 2, and more preferably 2.

n represents the average number of added moles of the alkyleneoxy group AO. n has an average value of 5 to 100 mol from the viewpoint of improving the stability of the aggregated particles and the fusing property of the resin particles, and improving the charging property, scattering property and heat-preserving property of the obtained toner. -50 mol is preferable, 9-30 mol is more preferable, 11-20 mol is still more preferable, and 12-15 mol is still more preferable.
AO represents an ethyleneoxy group and / or a propyleneoxy group, and A represents an ethylene group (—CH ₂ CH ₂ —) and / or a propylene group (—CH ₂ CH (CH ₃ ) — or —CH (CH ₃ ) CH. _2- ). A preferably contains an ethylene group or an ethylene group and a propylene group, and is preferably an ethylene group. When AO is a propyleneoxy group, the direction of the propylene group is not particularly limited.
When A is an ethylene group, n is an average value from the viewpoint of improving the stability of the aggregated particles and the fusing property of the resin particles, and improving the charging property, scattering property, and heat-preserving property of the obtained toner. Is 5 to 100 mol, preferably 6 to 50 mol, more preferably 9 to 30 mol, still more preferably 11 to 20 mol, and still more preferably 12 to 15 mol.

  M is ammonium, tetraalkylammonium, or alkali metal from the viewpoint of the particle size distribution of the obtained toner, preferably ammonium or alkali metal, and more preferably ammonium.

  Preferable sulfate ester salts include polyoxyethylene (5-100) distyrenated phenyl ether monosulfate ammonium salt, polyoxypropylene (5-95) polyoxyethylene (95-5) distyrenated phenyl ether monosulfate ammonium salt And polyoxyethylene (5-100) tribenzylated phenyl ether sulfate ammonium salt.

（式中、Ｒ¹は、水素原子又は炭素数１〜１２のアルキル基を表し、Ｒ²は、水素原子又はメチル基を表し、ｍは平均値が１〜４であり、ＡＯはエチレンオキシ基及び／又はプロピレンオキシ基を表し、ｎは平均値が５〜１００である。） Examples of the nonionic surfactant include nonionic surfactants represented by the following general formula (2), polyoxyethylene alkylaryl ethers or polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, and the like. A nonionic surfactant represented by the following general formula (2) is preferred.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a methyl group, m represents an average value of 1 to 4, and AO represents an ethyleneoxy group. And / or a propyleneoxy group, and n has an average value of 5 to 100.)

R ¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms from the viewpoint of improving the charging property, scattering property and heat-resistant storage stability of the toner. An atom or a methyl group is more preferable, and a hydrogen atom is still more preferable.

R ² represents a hydrogen atom or a methyl group from the viewpoint of improving the stability of the agglomerated particles and the fusing property of the resin particles, and improving the charging property, scattering property and heat-preserving property of the resulting toner. Is preferred. The plurality of R ² may be the same or different, but are preferably the same.
The nonionic surfactant represented by the general formula (2) may be a mixture of compounds in which m is any one of 1 to 4, and m has an average value of 1 to 4, From the viewpoint of improving the charging property, scattering property and heat-resistant storage stability, 2 to 3 is preferable and 2 is more preferable.
In the case where R ² is a hydrogen atom, the average value of m is preferably 2 to 3, and more preferably 3.
The average value of m when R ² is a methyl group is preferably 1 to 2, and more preferably 2.

n represents the average number of added moles of the alkyleneoxy group AO. n has an average value of 5 to 100 mol from the viewpoint of improving the stability of the aggregated particles and the fusing property of the resin particles, and improving the charging property, scattering property and heat-preserving property of the obtained toner. -50 mol is preferable, 9-30 mol is more preferable, 11-20 mol is still more preferable, and 12-15 mol is still more preferable.
AO represents an ethyleneoxy group and / or a propyleneoxy group, and A represents an ethylene group (—CH ₂ CH ₂ —) and / or a propylene group (—CH ₂ CH (CH ₃ ) — or —CH (CH ₃ ) CH. _2- ). A preferably contains an ethylene group or an ethylene group and a propylene group, and is preferably an ethylene group. When AO is a propyleneoxy group, the direction of the propylene group is not particularly limited.
When A is an ethylene group, n has an average value from the viewpoint of improving the stability of the aggregated particles and the fusing properties of the resin particles, and improving the chargeability, scattering properties and heat-resistant storage stability of the resulting toner. It is 5-100 mol, 6-50 mol is preferable, 9-30 mol is more preferable, 11-20 mol is still more preferable, 12-15 mol is still more preferable.
The HLB of the nonionic surfactant represented by the general formula (2) is preferably 10-18, more preferably 12-15.

Preferred nonionic surfactants represented by the general formula (2) include polyoxyethylene (5-100) distyrenated phenyl ether, polyoxypropylene (5-95) polyoxyethylene (95-5) distyrenated phenyl. And ethers and polyoxyethylene (5-100) tribenzylated phenyl ethers.
However, the number in parenthesis shows the average added mole number of polyoxyalkylene.

Examples of commercially available nonionic surfactants represented by the general formula (2) include polyoxyethylene (13) distyrenated phenyl ether (trade name: Emulgen A-60, manufactured by Kao Corporation), polyoxyethylene. (18) Distyrenated phenyl ether (trade name: Emulgen A-90, manufactured by Kao Corporation), polyoxyethylene (15) tribenzylated phenyl ether (trade name: Emulgen B-66, manufactured by Kao Corporation) It is done.
Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.

[Resin particles (B)]
In the present invention, the resin particles (B) preferably contain an amorphous polyester (b) from the viewpoints of heat resistant storage stability, scattering properties and chargeability of the toner.
The glass transition point of the resin particle (B) is appropriately determined depending on the glass transition point of the resin such as the amorphous polyester (b) constituting the resin particle (B), the kind and amount of the additive, etc. From the viewpoints of durability, low-temperature fixability, chargeability, scattering properties, and 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 more preferably 55 to 65 ° C. Further preferred.

The resin particles (B) preferably contain 70% by weight or more of amorphous polyester (b), more preferably 80% by weight or more, more preferably from the viewpoint of heat-resistant storage stability, scattering properties and chargeability of the toner. Contains 90% by weight or more, more preferably 95% by weight or more, and still more preferably 100% by weight.
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. .

(Amorphous polyester (b))
In the present invention, the amorphous polyester (b) is a polyester having a 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 less than 0.6, from the viewpoint of low-temperature fixability of the toner. It is 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 type and ratio of raw material monomers, production conditions (eg, reaction temperature, reaction time, cooling rate), and the like.
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 carboxyl group, a sulfonic acid group, a phosphonic acid group, and a sulfinic acid. Among these, a carboxyl group is preferable from the viewpoint of facilitating emulsification of the polyester.

  The amorphous polyester (b) can be produced by a polycondensation reaction between an acid component and an alcohol component in the same manner as the crystalline polyester (a).

Examples of the acid component include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, acid anhydrides thereof, and alkyl (C 1 -C 3) esters thereof, among which dicarboxylic acids are preferable.
Specific examples of the dicarboxylic acid include succinic acid, phthalic acid, isophthalic acid, terephthalic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Acid, sebacic acid, fumaric acid, maleic acid, adipic acid, azelaic acid, succinic acid, cyclohexanedicarboxylic acid and the like can be mentioned, among which fumaric acid, dodecenyl succinic acid and terephthalic acid are preferable, and dodecenyl succinic acid and terephthalic acid are more preferable.
Specific examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, and the like. Among these, from the viewpoint of offset resistance, trimellitic acid and its Acid anhydrides are preferred.
An acid component can be used individually or in combination of 2 or more types.
The amorphous polyester (b) is an acid component containing a trivalent or higher polyvalent carboxylic acid and its acid anhydride or alkyl ester, preferably trimellitic acid or its anhydride, from the viewpoint of offset resistance of the toner. It is preferable to use at least one amorphous polyester (b) obtained using

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 (2 to 3 carbon) oxide adduct (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.

The glass transition point of the amorphous polyester (b) is preferably 50 to 70 ° C., more preferably 55 to 68 ° C., from the viewpoint of toner durability, low-temperature fixability, chargeability, scattering properties and heat-resistant storage stability. 58-66 degreeC is still more preferable.
The softening point of the amorphous polyester (b) is preferably from 70 to 165 ° C, more preferably from 70 to 140 ° C, from the viewpoints of toner durability, low-temperature fixability, chargeability, scattering properties, and heat-resistant storage stability. -140 degreeC is still more preferable, and 100-130 degreeC is especially preferable.
In addition, when using 2 or more types of amorphous polyesters (b) mixed, the glass transition point and the softening point are each 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 from 1,000 to 50,000, more preferably from 1,500 to 10,000, from the viewpoint of toner durability, low-temperature fixability and heat-resistant storage stability. 2,000 to 8,000 are more preferable, and 2,000 to 4,000 are more preferable.
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 35 mgKOH / g, from the viewpoint of emulsification in the aqueous medium of the resin.

  The amorphous polyester (b) preferably contains two types of polyesters having different softening points from the viewpoints of low-temperature fixability, offset resistance, chargeability, scattering properties and durability of the toner. 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 weight 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 used to adjust the pH at 25 ° C. of the aqueous mixture used in the step of fusing the aggregated particles to a range of 2.0 to 5.0.
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 5.0 N, and more preferably 0.5 to 3.0 N. Here, “N” represents the normality of the acid (the acid concentration mol / liter multiplied by the equivalent amount).

<Method for producing electrophotographic toner>
The method for producing an electrophotographic toner of the present invention includes the following steps (1) to (3).
Step (1): After adjusting the pH at 25 ° C. of the aqueous mixed solution containing the aggregated particles including the resin particles (A) and the release agent particles and the surfactant to 2.0 to 5.0 and / or Or a step of fusing the aggregated particles in the aqueous mixed solution while adjusting,
Step (2): Step of adjusting the pH of the fused particle dispersion obtained in Step (1) at 25 ° C. to 5.5 to 7.5 Step (3): Fusion obtained in Step (2) Step of obtaining a toner particle by separating a liquid portion from a particle dispersion The aggregated particles used in the step (1) are aggregated by mixing resin particles (A), release agent particles and an aggregating agent in an aqueous medium. The resin particles (B) containing the amorphous polyester (b) are added to the step (1-1) for obtaining the aggregated particles (1) and the aggregated particles (1) obtained in the step (1-1). Thus, the agglomerated particles (2) obtained by the step (1-2) for obtaining the agglomerated particles (2) are preferable.
In the step of fusing the aggregated particles, the aggregated particles (2) are maintained at a temperature not lower than 10 ° C. and not higher than 5 ° C. below the glass transition point of the amorphous polyester (b). The step (1-4) for obtaining the attached core-shell particles is preferred.
Furthermore, although it is an optional step, it has a step (1-3) of adding the surfactant used in the step (1) after the step (1-2) and before the step (1-4). It is preferable.
Further, in the step (1-3) and / or the step (1-4), it is preferable to adjust the pH to 2.0 to 5.0 by adding an acid. From the viewpoint of improving the property and heat-resistant storage stability and suppressing scattering, it is preferable to adjust the pH to 2.0 to 5.0 by adding an acid in the step (1-3).

That is, the method for producing an electrophotographic toner of the present invention preferably includes the following steps (1-1) to (1-4).
Step (1-1): Step of mixing the resin particles (A), the release agent particles and the flocculant in an aqueous medium to obtain aggregated particles (1) Step (1-2): Step (1- Step of adding aggregated particles (1) obtained in 1) to resin particles (B) containing amorphous polyester (b) to obtain aggregated particles (2) Step (1-3): Surface activity Step of adding an agent Step (1-4): Temperature of the aggregated particles (2) not lower than a temperature 10 ° C. lower than the glass transition point of the amorphous polyester (b) and not higher than 10 ° C. higher than the glass transition point. In the step (1-3) and / or step (1-4), an acid is preferably added to adjust the pH to 2.0 to 5.0. adjust. That is, after adjusting the pH of the aqueous mixture to 2.0 to 5.0 in the step (1-3) and / or adjusting the pH of the aqueous mixture to 2.0 to 5.0 in the step (1-4). The aggregated particles in the aqueous mixed solution are fused while adjusting to obtain fused core-shell particles.
Hereinafter, each step will be described.

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

In this step, first, the resin particles (A) and the release agent particles are mixed in an aqueous medium to obtain a mixed dispersion.
In addition, although it is preferable to mix a colorant as an arbitrary component, the colorant may be mixed as a separate particle by itself, or may be contained in the resin particles (A). Therefore, it is preferably contained in 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 the mixed dispersion, the resin particles (A) are preferably 10 to 40 parts by weight, and more preferably 20 to 30 parts by weight. The aqueous medium is preferably 60 to 90 parts by weight, and more preferably 70 to 80 parts by weight.
Moreover, 1-20 weight part is preferable with respect to 100 weight part of resin which comprises a resin particle (A) from a viewpoint of image density, and, as for a coloring agent, 3-15 weight part is more preferable. The release agent particles are preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the total of the resin and the colorant, from the viewpoint of toner releasability and chargeability.
The mixing temperature is preferably 0 to 40 ° C. from the viewpoint of aggregation control.

Next, the particles in the mixed dispersion are aggregated to obtain a dispersion of aggregated particles (1). It is preferable to add a flocculant for efficient aggregation.
As the flocculant, a quaternary salt cationic surfactant, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as an inorganic metal salt, an inorganic ammonium salt, or a bivalent or higher metal complex are 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 use amount of the flocculant is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and further preferably 30 parts by weight with respect to 100 parts by weight of the resin constituting the resin particles (A), from the viewpoint of chargeability of the toner. Less than parts by weight. From the viewpoint of the cohesiveness of the resin particles, the amount is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and still more preferably 5 parts by weight or more with respect to 100 parts by weight of the resin constituting the resin particles (A). is there. In consideration of the above points, the amount of the monovalent salt used is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the resin constituting the resin particles (A). More preferably, it is 5-30 weight part.

  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.

  The volume median particle size of the obtained agglomerated particles (1) is preferably 1 to 10 μm, more preferably 2 from the viewpoint of reducing the particle size and reducing the amount of scattering of the resulting toner in a printing machine such as a printer. It is -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.

[Step (1-2)]
In step (1-2), resin particles (B) containing amorphous polyester (b) are added to the aggregated particles (1) obtained in step (1-1) to obtain aggregated particles (2). It is the process of obtaining.
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 (1-1) to obtain aggregated particles. It is preferable that the resin particles (B) are further adhered to (1) 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 toner productivity and manufacturing simplicity, 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 5 ° C. or more lower than the melting point of the crystalline polyester (a) contained in the resin particles (A) from the viewpoint of low-temperature fixability of the toner, heat-resistant storage stability and reduction in the amount of scattering. The glass transition point of the crystalline polyester (b) is preferably 3 ° C. or more, more preferably 5 ° C. or more. 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 a weight ratio of the resin particles (B) to the resin particles (A) (resin particles (B) / The amount of the resin particles (A)) is preferably 0.3 to 1.5, more preferably 0.3 to 1.0, and still more preferably 0.35 to 0.75.

  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 from the viewpoint of shortening the production time.

The volume median particle size of the aggregated particles (2) obtained in the step (1-2) is preferably 1 to 10 μm, more preferably 2 to 10 μm from the viewpoint of obtaining a toner capable of obtaining a high quality image. 3 to 9 μm is more preferable, and 4 to 6 μm is more preferable.
The pH of the aggregated particles (2) obtained in the step (1-2) is preferably 5.5 to 7.5, more preferably 6.0 to 7.0, and 6.0 to 6.5. Further preferred.

[Step (1-3)]
Step (1-3) is a step of adding the surfactant used in step (1). In step (1-3), it is preferable to adjust the pH of the dispersion to 2.0 to 5.0 by adding an acid to the dispersion of aggregated particles (2) obtained in step (1-2). .
The addition amount of the surfactant is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the resin in the system from the viewpoint of suppressing the generation of coarse particles and reducing the remaining of the surfactant. Part by weight is more preferable, and 1.5 to 5 parts by weight is even more preferable.
The temperature at which the surfactant and the 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 further preferably 25 ° C to 45 ° C. is there.
In this step, when an acid is added, the surfactant and the acid may be mixed and added, or may be added separately. When they are added separately, any of them may be added first, but 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 due to the addition of the acid, but the fusion property of the resin particles and the stability of the aggregated particles, that is, the fusion between the aggregated particles. From the viewpoint of preventing adhesion, and thus improving the low-temperature fixability, charging property, scattering property and heat-resistant storage stability of the resulting toner, an acid is added so that the pH of the dispersion becomes 2.0 to 5.0. It is preferable that 2.5 to 4.5 is more preferable, 2.5 to 4.0 is more preferable, and it is still more preferable to add an acid so as to be 3.0 to 4.0.

[Step (1-4)]
In the step (1-4), the agglomerated particles (2) are held at a temperature not lower than 10 ° C. and not higher than 10 ° C. below the glass transition point of the amorphous polyester (b), and fused core-shell particles. If the acid is not added in step (1-3), the acid should be added in this step. Is preferred.
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 viewpoints of fusing property and toner productivity, in this step, the temperature is 8 ° C. or more lower than the glass transition point of the amorphous polyester (b), preferably 6 ° C. or more, more preferably 5 ° C. It is more preferable that the temperature is kept at a temperature not lower than 0 ° C. From the viewpoint of improving heat-resistant storage stability and chargeability and suppressing toner scattering, in this step, the glass transition point of the amorphous polyester (b) is 10 Hold at a temperature not higher than the glass transition temperature, preferably not higher than 8 ° C., more preferably not higher than 6 ° C., more preferably not higher than 3 ° C., more preferably not higher than the glass transition temperature. Is more preferable.
Further, from the viewpoint of heat-resistant storage stability, scattering property and charging property of the toner, in this step, the temperature is 5 ° C. or lower, preferably 7 ° C. or lower, more preferably 10 ° C. lower than the melting point of the crystalline polyester (a). More preferably, the temperature is kept at a low temperature or lower.
Furthermore, from the viewpoints of fusing property, heat-resistant storage stability of toner, charging property, scattering property, and toner productivity, in this step, the glass transition temperature is at least 5 ° C. lower than the glass transition point of the resin particles (B). It is preferable to hold at a temperature not higher than 10 ° C. below the point.
Also, from the viewpoint of toner chargeability and scattering properties, in this step, the temperature is maintained at a temperature 5 ° C. or more lower than the melting point of the release agent, preferably 7 ° C. or less, more preferably 10 ° C. or less. Is more preferable.
In this step, from the viewpoint of particle fusibility, the temperature is preferably 55 to 70 ° C, more preferably 57 to 65 ° C, and still more preferably 58 to 62 ° C.
The pH of the dispersion in this step is 2.0 to 5.0 from the viewpoint of preventing the fusion of the resin particles and the stability of the aggregated particles, that is, the fusion between the aggregated particles, and 2.5 to 4 0.5 is preferable, 2.5 to 4.0 is more preferable, and 3.0 to 4.0 is 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 2.0 to 5.0, and 2.5 to 4.5 More preferably, 2.5-4.0 is more preferable, and it is still more preferable to add an acid so that it may become 3.0-4.0.

The holding time in this step is preferably from 1 to 24 hours, more preferably from 1 to 18 hours, still more preferably from 2 to 12 hours, from the viewpoints of particle fusing property, heat-resistant storage stability, chargeability and toner productivity. Preferably it is 2 to 5 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, preferably 0.958 to 0.985, and preferably 0.960 to 0.85 from the viewpoints of scattering properties and cleaning properties of the obtained toner. 985 is more preferable, and 0.965 to 0.980 is even more preferable.
The degree of circularity of the fused core-shell particles is preferably 0.01 or more larger than the degree of circularity of the agglomerated particles (2) from the viewpoint of improving the heat-resistant storage stability of the toner and suppressing scattering. More preferably, it is more preferably 0.015 or more.
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 is suppressed.
BET specific surface area by nitrogen adsorption method of fusing the core-shell particles, 1.0~5.0m ² / g from the viewpoints of charging property and the heat-resistant storage stability of the toner obtained is preferably, 1.0~4.0m ² / g, more preferably, 1.0～3.5M more preferably ² / g, more preferably 1.3~2.3m ² / g.

From the viewpoint of improving the image quality of the 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, more preferably 2 to 7 μm, still more preferably 3 to 8 μm. More preferably, it is 4-6 micrometers.
The average particle size of the fused core-shell particles obtained in this step is preferably equal to or less than the average 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.

[Step (2)]
In the present invention, step (2) is performed after step (1). In particular, it is preferable to perform the step (2) after the step (1-4).
Step (2) is a step of adjusting the pH at 25 ° C. of the fused particle dispersion obtained in step (1-4) among steps (1) to 5.5 to 7.5.
In this step, the pH of the dispersion to be adjusted at 25 ° C. is 5.5 to 7.5 from the viewpoint of heat-resistant storage stability of the toner, scattering properties, and chargeability under high temperature and high humidity. It is preferably -7.3, more preferably 5.7-7.2, and more preferably 6.5-7.1.
In this step, it is preferable to use a base for adjusting the pH, and it is more preferable to use an alkali metal hydroxide, a water-soluble amine, or an organic ammonium hydroxide as the base. Of these, alkali metal hydroxides and water-soluble amines are preferred from the viewpoint of heat-resistant storage stability of the toner, and alkali metal hydroxides are more preferred.
As the alkali metal hydroxide, potassium hydroxide and sodium hydroxide are preferable.
Examples of the water-soluble amine include alcohol amines having 1 to 3 carbon atoms, alcohol amines having 2 carbon atoms are preferable, and triethanolamine is more preferable.
As a method for adding the base, it is preferable to add it as an aqueous solution to the fused particle dispersion obtained in the step (1).
The concentration of the aqueous solution is preferably 0.1 to 30% by weight and more preferably 1 to 10% by weight from the viewpoint of heat-resistant storage stability of the toner.
In this step, the toner is preferably kept at 55 to 70 ° C., more preferably 57 to 65 ° C., and further preferably 58 to 62 ° C., from the viewpoints of heat-resistant storage stability, scattering properties, and chargeability under high temperature and high humidity. To do.

  The holding time at the temperature in this step is preferably 0.1 to 10 hours, more preferably 0.3 to 5 hours, from the viewpoints of heat-resistant storage stability, scattering properties and chargeability under high temperature and high humidity. It is. In addition, it is preferable to stir while hold | maintaining at the said temperature, and it is preferable to cool to 20-30 degreeC after holding | maintenance time progress.

[Step (3)]
Step (3) is a step of obtaining toner particles by removing the liquid portion from the fused particle dispersion obtained in step (2).
In this step, since the fused particles obtained in step (2) are present in the aqueous medium as a dispersion, the liquid portion is removed in this step. This step is performed for the purpose of removing the surfactant and the like on the surface of the toner particles and ensuring charging characteristics.

As a method for removing the liquid portion, a pressure filtration method, a vacuum filtration method, and a centrifugal separation method are preferably used, a pressure filtration method is more preferred, and a pressure filtration method and a vacuum filtration method may be used in combination. Further preferred.
A preferable pressure filtration method includes a method using a filter press, and a preferable vacuum filtration method includes a suction filtration method using a Buchner funnel.

In this step, it is preferable to perform washing while removing the liquid part or after removing the liquid part. In particular, when removing the liquid part using a pressure filtration method, a suction filtration method, and a centrifugal separation method, It is preferable to pass the solvent used for washing through the layer of the fused particles from which the components have been removed.
An aqueous solvent is preferably used for washing, and water is particularly preferable, and specifically, deionized water is preferably used.
When water is passed through the layer of fused particles, it is preferable that the discharged water has a conductivity of 1.0 mS / m or less, preferably 0.5 mS / m or less. Is more preferable.
When the pressure filtration method and the vacuum filtration method are used in combination, it is preferable to obtain a cake-like material containing moisture by pressure filtration, and further remove the moisture by vacuum filtration of the obtained cake-like material.

  Next, drying is preferably performed, and the drying method is not limited. However, it is preferable to dry the cake by passing a gas through it. The drying temperature is preferably set so that the temperature of the fused particles themselves is 5 ° C. or more lower than the melting point of the crystalline polyester, and more preferably 10 ° C. or more. The water content after drying is preferably adjusted to 1.5% by weight or less, more preferably 1.0% by weight or less, from the viewpoint of reducing the amount of toner scattered and charging properties.

<Toner for electrophotography>
(toner)
The toner particles obtained by drying or the like can be used as they are as the toner of the present invention, but it is preferable to use toner particles whose surface has been treated as described below as the toner for electrophotography.
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 low-temperature fixability of the toner. The glass transition point is preferably 30 to 80 ° C, more preferably 40 to 70 ° C, from the viewpoints of low-temperature fixability, durability, and heat-resistant storage stability.
The circularity of the toner is preferably 0.955 to 0.985, more preferably 0.955 to 0.980, and still more preferably 0.965 to 0, from the viewpoint of heat resistant storage stability, scattering properties, and cleaning properties of the toner. .980. The circularity of the toner particles can be measured by the method described later. The circularity of the toner particles is a value obtained by a ratio of the circumference of the circle equal to the projected area / the circumference of the projected image. The more circular the particles are, the closer the circularity is to 1. .
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 weight, more preferably 70 to 100% by weight, and still more preferably 90 to 90%. Contains 100% by weight.
The volume median particle size of the toner is preferably 1 to 10 μm, more preferably 2 to 8 μm, still more preferably 3 to 7 μm, and still more preferably 4 to 6 μm, from the viewpoint of high image quality and productivity of the toner.
The CV value of the toner is preferably 30% or less, more preferably 27% or less, still more preferably 25% or less, and further preferably 22% or less, from the viewpoint of high image quality and productivity.

(External additive)
In the electrophotographic toner 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 weight, more preferably 100 parts by weight of the toner particles before the treatment with the external additive. 1 to 3.5 parts by weight, more preferably 1 to 3 parts by weight.

  The toner for electrophotography obtained by the present invention can be used as a one-component developer or as a two-component developer by mixing with a carrier.

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

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

[Polyester softening point, endothermic maximum peak temperature, melting point and glass transition point]
(1) Softening point Using a flow tester (manufactured by Shimadzu Corporation, trade name: CFT-500D), a load of 1.96 MPa was applied by a plunger while heating a 1 g sample at a heating rate of 6 ° C / min. And extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. The amount of flow tester drop by the flow tester was plotted against the temperature, and the temperature at which half the sample flowed out was taken as the softening point.
(2) Endothermic maximum peak temperature, melting point and glass transition point Using a differential scanning calorimeter (manufactured by PerkinElmer, trade name: Pyris 6 DSC), the temperature is raised to 200 ° C., and the temperature lowering rate is 50 ° C./min. The sample cooled to 0 ° C. was measured at a heating rate of 10 ° C./min. Of the endothermic peaks observed, the peak temperature having the maximum peak area was defined as the maximum endothermic peak temperature. 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 glass transition point was defined as the temperature at the intersection with the base line extension line on the high temperature side.

[Glass Transition Point of Resin Particle (B) Containing Amorphous Polyester (b)]
When measuring the glass transition point of the resin particles (B), the solvent was removed from the dispersion of the resin particles (B) by freeze-drying, and the obtained solid was measured by the above method.
The lyophilization of the dispersion of the resin particles (B) is performed using a freeze dryer (trade name: FDU-2100 and DRC-1000, manufactured by Tokyo Rika Kikai Co., Ltd.), and 30 g of the dispersion of resin particles (B). Vacuum drying was performed 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 became 1% by weight or less. The moisture content was determined by using an infrared moisture meter (trade name: FD-230, manufactured by Kett Scientific Laboratory), drying 5 g of the sample at a drying temperature of 150 ° C. and a measurement mode 96 (monitoring time 2.5 minutes). / Fluctuation range 0.05%).
The method for measuring the glass transition point was the same as the method for measuring the glass transition point 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 (manufactured by Sumitomo Electric Industries, Ltd., trade name: FP-200) to remove insoluble components to obtain a sample solution.
(2) Molecular weight distribution measurement Chloroform was allowed to flow as a lysis solution 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. In the calibration curve at this time, 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 Industries, Ltd.)
Analytical column: JAIGEL-2.5-HA + JAIGEL-MH-A (both trade names, manufactured by Nippon Analytical Industries, Ltd.)

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution of Resin Particles, Release Agent Particles]
(1) Measuring device: Laser diffraction particle size measuring machine (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 average 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 weight) = 100-M
M: moisture (%) = [(W−W ₀ ) / W] × 100
W: Sample weight before measurement (initial sample weight)
W ₀ : Sample weight after measurement (absolute dry weight)

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution 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 weight.
-Dispersion condition: 10 mg of a toner measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution thereof. From this, the volume median particle size (D ₅₀ ) was determined.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100
The volume-median particle size of the agglomerated particles and the agglomerated particles (2) is the same when the agglomerated particle dispersion and the agglomerated particles (2) are used as the sample dispersion in the measurement of the volume-median particle size of the toner (particles). Measured.

[Core shell particle, toner circularity]
-Preparation of dispersion: The dispersion of core-shell particles was prepared by diluting with deionized water so that the solid content concentration of the core-shell particles was 0.001 to 0.05%. The toner dispersion was prepared by adding 50 mg of toner to 5 ml of 5% by weight polyoxyethylene lauryl ether (Emulgen 109P) aqueous solution, dispersing for 1 minute with an ultrasonic disperser, and then adding 20 ml of distilled water. It was prepared by dispersing for 1 minute with a sonic disperser.
Measurement 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 sample amount: 0.09 to 0.11 g
・ Deaeration condition: 40 ° C., 10 minutes ・ Adsorption gas: Nitrogen gas

[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. A solid image of / cm ² 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.
After lightly pasting a mending tape (product name: Scotch mending tape 810, width 18 mm) cut to a length of 50 mm from the margin at the top of the printed image to the solid image portion, A weight of 500 g was placed and pressed once back and forth at a speed of 10 mm / second. Thereafter, the affixed tape was peeled off from the lower end side at a peeling angle of 180 degrees and a speed of 10 mm / second to obtain a printed matter after the tape was peeled off. 30 sheets of high quality paper (Oki Data Co., Ltd., Excellent White Paper A4 size) is placed under the printed material before and after the tape is applied, and the reflected image density of the fixed image portion before and after the tape is applied to each printed material. , Measured using a colorimeter (GretagMacbeth, trade name: SpectroEye, light emission condition: standard light source D ₅₀ , observation field of view 2 °, density standard DINNB, absolute white standard) Calculated.
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 24 hours 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 is set on a powder tester (trade name, manufactured by Hosokawa Micron Co., Ltd.), and 20 g of the toner is placed on the shaker for 30 seconds. The remaining toner weight on the sieve is measured. It 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 of 25 ° C. and 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. And shaken 10 times each. Then, it stirred for 10 minutes with the ball mill.
An external developing roller device in which a developing roller (42 mm in diameter) mounted on a commercially available printer (trade name: Microline 5400, manufactured by Oki Data Co., Ltd.) was taken out and modified 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 was deposited on the developing roller. After uniformly attaching, the rotation was once stopped. The number of scattering toner particles when the rotation speed of the developing roller was changed to 45 rotations / minute and rotated for 1 minute was measured with a digital dust meter (manufactured by Shibata Kagaku Co., Ltd., model: P-5).
The toner scattering property was evaluated from the number of scattered toner particles. The scattering property indicates that the smaller the toner scattering particle number, the better.

[Evaluation of chargeability of toner at normal temperature and normal humidity (under NN environment)]
At 50 ° C. and 50% relative humidity, 2.1 g of toner and 27.9 g of a silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size: 40 μm) and a 50 cc cylindrical polypropylene bottle (manufactured by Nikko Corporation) ) And shaken 10 times vertically and horizontally, and then mixed at a speed of 90 r / min using a tumbler mixer and mixed for 1 hour. The charge amount at that time was measured using a q / m meter (manufactured by EPPING). The higher the absolute value of the charge amount, the better the chargeability.
Measurement equipment, settings, etc. are as follows.
Measuring instrument: q / m-meter manufactured by EPPING
Setting: Mesh size: 635 mesh (aperture: 24 μm, made of stainless steel)
Soft blow, blow pressure (1000V)
Suction time: 90 seconds Charge amount (μC / g) = Total amount of electricity after 90 seconds (μC) / Amount of toner sucked (g)

[Evaluation of chargeability of toner at high temperature and high humidity (HH environment)]
The toner after chargeability evaluation at room temperature and normal humidity was placed at an air temperature of 30 ° C. and a relative humidity of 85% (high temperature and high humidity environment) and held for 12 hours. Thereafter, the mixture was placed in a high temperature and high humidity environment at a temperature of 25 ° C. and a relative humidity of 50%. The higher the absolute value of the charge amount, the better the chargeability.

[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, melting point, crystallinity index, 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, melting point, crystallinity index, 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, glass transition point, crystallinity index, 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 measured according to ASTM D36-86 reached 120 ° C., the temperature was lowered to stop the reaction. Amorphous polyester Y2 was obtained. Table 1 shows the softening point, glass transition point, crystallinity index, 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 reaction was continued until the desired softening point was reached to obtain amorphous polyester Y3. Table 1 shows the softening point, glass transition point, crystallinity index, 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 dispersion of resin particles (A-1))
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.), polyoxy Ethylene alkyl 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) 80 g of Kao Co., Ltd.) and 266 g of 5 wt% aqueous potassium hydroxide solution 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, volume median particle size, and CV value of the obtained resin particle dispersion.

Production Example 7
(Preparation of dispersion of resin particles (A-2))
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, copper phthalocyanine pigment (trade name: ECB301, manufactured by Dainichi Seika Kogyo Co., Ltd.), polyoxy Ethylene alkyl 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) 80 g of 5% by weight potassium hydroxide aqueous solution was 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, 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, volume median particle size, and CV value of the obtained resin particle dispersion.

Production Example 8
(Preparation of dispersion of resin particles (B-1))
In a flask equipped with a stirrer, 390 g of amorphous polyester Y1, 210 g of amorphous polyester Y2, polyoxyethylene alkyl ether (nonionic surfactant, trade name: Emulgen 430, manufactured by Kao Corporation), 6 g, 15 weight 40% of sodium dodecylbenzenesulfonate aqueous solution (anionic surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation) and 268 g of 5 wt% potassium hydroxide were added, and the temperature was raised to 95 ° C while stirring. The mixture was melted and 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 is cooled to 25 ° C., passed through a 200-mesh wire mesh, deionized water is added, and the solid content is adjusted to 23.5 wt%. ) Dispersion was obtained. Table 2 shows the solid content concentration, volume median particle size, and CV value of the obtained resin particle dispersion.

Production Example 9
(Preparation of dispersion of resin particles (B-2))
In a flask equipped with a stirrer, 600 g of amorphous polyester Y3, 6 g of polyoxyethylene alkyl ether (nonionic surfactant, trade name: Emulgen 430, manufactured by Kao Corporation), 15% by weight sodium dodecylbenzenesulfonate aqueous solution (Anionic surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation) 40 g and 247 g of 5 wt% potassium hydroxide were added, and the mixture was heated to 95 ° C. and melted with stirring. For 2 hours to obtain a resin mixture.
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 to adjust the solid content to 23.5 wt%, and the resin particles (B-2) A dispersion was obtained. Table 2 shows the solid content concentration, volume median particle size, and CV value of the obtained resin particle dispersion.

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: Latemulu ASK, Kao Corporation, effective concentration 28 wt%), 120 g of carnauba wax (produced by Hiroyuki Kato, melting point 85 ° C., acid value 5 mgKOH / g) was added and stirred. While maintaining the mixed liquid at 90 to 95 ° C., it was subjected to a dispersion treatment for 30 minutes using an ultrasonic disperser (trade name: Ultrasonic Homogenizer 600W, manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then cooled to 25 ° C. Then, deionized water was added to adjust the solid content to 20% by weight 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 surfactant]
Production Example 11
(Synthesis of Surfactant 1 (Polyoxyethylene (13) Distyrenated Phenyl Ether Monosulfate Ammonium Salt))
608 g (2 mol) of distyrenated phenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 0.56 g (0.01 mol) of potassium hydroxide were charged into an autoclave equipped with a stirrer, a temperature controller and an ethylene oxide introduction device. Water was removed at 1.3 ° C. and 30 ° C. for 30 minutes. Thereafter, nitrogen substitution was carried out, and after raising the temperature to 145 ° C., 1144 g (26 mol) of ethylene oxide was charged. The addition reaction was carried out at 145 ° C. until the pressure became constant, and aging was carried out at 145 ° C. for 1 hour, followed by cooling to 80 ° C. Next, an inorganic alkali adsorbent was added, and potassium hydroxide was removed by filtration to obtain polyoxyethylene (13) distyrenated phenol having an average addition mole number of ethylene oxide of 13 moles (however, The numbers in parentheses indicate the average number of moles of ethylene oxide added, and so on.
438.0 g (0.5 mol) of this polyoxyethylene (13) distyrenated phenol was charged into a reactor equipped with a stirrer and a temperature controller, and water was removed at 110 ° C. and 1.3 kPa for 30 minutes. . After cooling to 80 ° C., 46.1 g (0.475 mol) of sulfamic acid was charged, the temperature was raised to 110 ° C., the mixture was reacted for 3 hours, and polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (surfactant) Agent 1) was obtained.

Production Example 12
(Synthesis of surfactant 2 (polyoxyethylene (20) distyrenated phenyl ether monosulfate ammonium salt))
608 g (2 mol) of distyrenated phenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 0.56 g (0.01 mol) of potassium hydroxide were charged into an autoclave equipped with a stirrer, a temperature controller and an ethylene oxide introduction device. Water was removed at 30 ° C. and 1.3 kPa for 30 minutes. Thereafter, nitrogen substitution was carried out, and after raising the temperature to 145 ° C., 1760 g (40 mol) of ethylene oxide was charged. The addition reaction was carried out at 145 ° C. until the pressure became constant, and aging was carried out at 145 ° C. for 1 hour, followed by cooling to 80 ° C. Next, an inorganic alkali adsorbent was added, and potassium hydroxide was removed by filtration to obtain polyoxyethylene (20) distyrenated phenol having an average added mole number of ethylene oxide of 20 mol.
The polyoxyethylene (20) distyrenated phenol 592.0 g (0.5 mol) was charged into a reactor equipped with a stirrer and a temperature controller, and water was removed at 110 ° C. and 1.3 kPa for 30 minutes. . After cooling to 80 ° C., 46.1 g (0.475 mol) of sulfamic acid was added, the temperature was raised to 110 ° C., the mixture was reacted for 3 hours, and polyoxyethylene (20) distyrenated phenyl ether monosulfate ammonium salt (surfactant) Agent 2) was obtained.

Production Example 13
(Synthesis of surfactant 3 (polyoxypropylene (3) polyoxyethylene (10) distyrenated phenyl ether monosulfate ammonium salt))
608 g (2 mol) of distyrenated phenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 0.56 g (0.01 mol) of potassium hydroxide were charged into an autoclave equipped with a stirrer, a temperature controller and an ethylene oxide introduction device. Water was removed at 30 ° C. and 1.3 kPa for 30 minutes. Thereafter, nitrogen substitution was performed, the temperature was raised to 120 ° C., and then 348 g (6 mol) of propylene oxide was charged. The addition reaction was carried out at 120 ° C. until the pressure became constant. After aging at 120 ° C. for 1 hour, moisture was removed at 110 ° C. and 1.3 kPa for 30 minutes. Thereafter, nitrogen substitution was performed and the temperature was raised to 145 ° C., and then 880 g (20 mol) of ethylene oxide was charged. The addition reaction was performed at 145 ° C. until the pressure became constant, and the mixture was aged for 1 hour at this temperature, and then cooled to 80 ° C. Next, an inorganic alkali adsorbent is added, and the potassium hydroxide is removed by filtration. Polyoxypropylene (3 ) Polyoxyethylene (10) distyrenated phenol was obtained.
459.0 g (0.5 mol) of this polyoxypropylene (3) polyoxyethylene (10) distyrenated phenol was charged into a reactor equipped with a stirrer and a temperature controller, and 110 minutes at 110 ° C. and 1.3 kPa. Water was removed. After cooling to 80 ° C., 46.1 g (0.475 mol) of sulfamic acid was charged, the temperature was raised to 110 ° C., and the mixture was reacted for 3 hours to obtain polyoxypropylene (3) polyoxyethylene (10) distyrenated phenyl ether monosulfate An ester ammonium salt (Surfactant 3) was obtained.

Production Example 14
(Synthesis of surfactant 4: polyoxyethylene (10) tribenzylated phenyl ether sulfate ammonium salt)
A tribenzylated phenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) 592 g (2 mol) and 0.56 g (0.01 mol) of potassium hydroxide were charged into an autoclave equipped with a stirrer, a temperature controller and an ethylene oxide introduction device. Water was removed at 30 ° C. and 1.3 kPa for 30 minutes. Thereafter, nitrogen substitution was performed, the temperature was raised to 145 ° C., and then 880 g (20 mol) of ethylene oxide was charged. The addition reaction was carried out at 145 ° C. until the pressure became constant, and aging was carried out at 145 ° C. for 1 hour, followed by cooling to 80 ° C. Next, an inorganic alkali adsorbent was added, and the potassium hydroxide was removed by filtration to obtain polyoxyethylene (10) tribenzylated phenol having an average added mole number of ethylene oxide of 10 mol.
368.0 g (0.5 mol) of this polyoxyethylene (10) tribenzylated phenol was charged into a reactor equipped with a stirrer and a temperature controller, and water was removed at 110 ° C. and 1.3 kPa for 30 minutes. . After cooling to 80 ° C., 46.1 g (0.475 mol) of sulfamic acid was added, the temperature was raised to 110 ° C., the mixture was reacted for 3 hours, and polyoxyethylene (10) tribenzylated phenyl ether sulfate ammonium salt (surfactant) 4) was obtained.

Production Example 15
(Synthesis of Surfactant 5: Polyoxyethylene (7) Distyrenated (Methyl) Phenyl Ether Monosulfate Ammonium Salt)
313.0 g (0.5 mol) of polyoxyethylene (7) distyrenated methylphenol was charged into a reactor equipped with a stirrer and a temperature controller, and water was removed at 110 ° C. and 1.3 kPa for 30 minutes. . After cooling to 80 ° C., 46.1 g (0.475 mol) of sulfamic acid was added, the temperature was raised to 110 ° C., and the mixture was reacted for 3 hours. Activator 5) was obtained.

[Production of toner]
Example 1
(Preparation of Toner A)
<Step (1-1): Production of Aggregated Particle (1)>
In a four-necked flask having an internal volume of 10 liters equipped with a dehydrating tube, a stirrer, and a thermocouple, 600 g of a dispersion of resin particles (A-1), 162 g of deionized water, and 101 g of a release agent particle dispersion are placed at a temperature of 25. Mixed under ℃. Next, while stirring the mixture, an aqueous solution in which 50 g of ammonium sulfate was dissolved in 525 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 (1-2): Production of Aggregated Particle (2)>
97 g of deionized water was added to the dispersion (total amount) of the aggregated particles (1) obtained in the step (1-1), and the temperature of the dispersion of aggregated particles (1) was cooled to 49 ° C. Next, while heating the dispersion at 49 ° C. at a rate of 1.6 ° C. per hour, 380 g of the dispersion of resin particles (B-1) was dropped at a rate of 1.2 ml per minute, and the aggregated particles (2) A dispersion was 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 (1-3): 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 (1-2), 8.3 g of polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (surfactant 1) and deionized An aqueous solution mixed with 8003 g of water was added. Thereafter, 2.0 N sulfuric acid was added so that the pH at 25 ° C. was 3.5.

<Step (1-4): Fusion Step of Aggregated Particle (2)>
The dispersion liquid of the aggregated particles (2) whose pH was adjusted in the step (1-3) was heated to 60 ° C., held at 60 ° C. for 3 hours, and the particles were fused to obtain core-shell particles.

<Step (2): Adjustment of pH of core-shell particle dispersion>
A 20 wt% aqueous potassium hydroxide solution was added to the core-shell particle dispersion obtained in step (1-4) so that the pH at 25 ° C. was 7.0. Thereafter, the core-shell particle dispersion was held at 60 ° C. with stirring for 1 hour, and then cooled to 25 ° C.

<Process (3): Filtration and washing process of core-shell particle dispersion>
The obtained dispersion was supplied to a filter press machine (manufactured by Ataca Daiki Co., Ltd., model name: TFP-3 type) at 0.3 MPa, and filtered to form a cake layer. Deionized water was allowed to penetrate therethrough at 0.5 MPa, and washing was performed until the conductivity of the discharged filtrate was 0.5 mS / m or less. Thereafter, the cake layer was squeezed at 0.7 MPa until the filtrate disappeared, the toner cake layer was taken out, suction filtered using a Buchner funnel, ventilated with air, and dried to obtain toner particles. Table 3 shows the circularity, the BET specific surface area, and the volume-median particle size of the obtained toner particles.

<External addition process>
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, Cabot Corporation) Manufactured, average particle size; 0.012 μm) was put in a Henschel mixer, stirred, and passed through a 150-mesh sieve to obtain toner A. The obtained toner evaluation is shown in Table 3.

Example 2
(Preparation of Toner B)
A toner was produced in the same manner as in Example 1 except that the steps (1-1) to (1-4) were changed as follows. Table 3 shows the physical properties and toner evaluation of the obtained toner.
<Step (1-1): Production of Aggregated Particle (1)>
In a four-necked flask with an internal volume of 10 liters equipped with a dehydrating tube, a stirrer, and a thermocouple, 600 g of a dispersion of resin particles (A-2), 134 g of deionized water, and 97 g of a release agent particle dispersion were added at a temperature of 25. Mixed under ℃. Next, while stirring the mixture, an aqueous solution in which 49 g of ammonium sulfate was dissolved in 506 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 (1-2): Production of Aggregated Particle (2)>
94 g of deionized water was added to the dispersion (total amount) of the aggregated particles (1) obtained in the step (1-1), and the temperature of the dispersion of aggregated particles (1) was cooled to 49 ° C. Next, while the temperature of the dispersion at 49 ° C. was increased at a rate of 1.6 ° C./hour, 367 g of the dispersion of resin particles (B-1) was added dropwise at a rate of 1.2 ml / min. A dispersion was 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 (1-3): Addition of surfactant to dispersion of aggregated particles (2) and adjustment of pH>
In a dispersion (total amount) of the aggregated particles (2) obtained in the step (1-2), 8.0 g of polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (surfactant 1) and deionized An aqueous solution mixed with 7713 g of water was added. Thereafter, 2.0 N sulfuric acid was added so that the pH at 25 ° C. was 3.5.

<Step (1-4): Fusion Step of Aggregated Particle (2)>
The dispersion liquid of the aggregated particles (2) whose pH was adjusted in the step (1-3) was heated to 60 ° C., held at 60 ° C. for 3 hours, and the particles were fused to obtain core-shell particles.

Example 3
(Preparation of toner C)
A toner was prepared in the same manner as in Example 1 except that in the step (2), the time for holding the core-shell particle dispersion at 60 ° C. with stirring was 15 minutes. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 4
(Preparation of Toner D)
A toner was prepared in the same manner as in Example 1 except that the step (2) was changed as follows. Table 3 shows the physical properties and toner evaluation of the obtained toner.
<Step (2): Adjustment of pH of core-shell particle dispersion>
The core-shell particle dispersion obtained in step (1-4) was cooled to 55 ° C., and a 20 wt% aqueous potassium hydroxide solution was added so that the pH at 25 ° C. was 7.0. Thereafter, the core-shell particle dispersion was held at 55 ° C. with stirring for 1 hour, and then cooled to 25 ° C.

Example 5
(Production of Toner E)
A toner was prepared in the same manner as in Example 1 except that the step (2) was changed as follows. Table 3 shows the physical properties and toner evaluation of the obtained toner.
<Step (2): Adjustment of pH of core-shell particle dispersion>
The core-shell particle dispersion obtained in step (1-4) was cooled to 40 ° C., and a 20 wt% aqueous potassium hydroxide solution was added so that the pH at 25 ° C. was 7.0. Thereafter, the core-shell particle dispersion was held at 40 ° C. with stirring for 1 hour, and then cooled to 25 ° C.

Example 6
(Production of Toner F)
A toner was prepared in the same manner as in Example 1 except that the step (2) was changed as follows. Table 3 shows the physical properties and toner evaluation of the obtained toner.
<Step (2): Adjustment of pH of core-shell particle dispersion>
The core-shell particle dispersion obtained in the step (1-4) was cooled to 25 ° C., and a 20 wt% aqueous potassium hydroxide solution was added so that the pH at 25 ° C. was 7.0. Thereafter, the core-shell particle dispersion was held at 25 ° C. with stirring for 1 hour.

Example 7
(Preparation of toner G)
A toner was prepared in the same manner as in Example 1 except that in the step (2), a 20 wt% aqueous potassium hydroxide solution was added so that the pH at 25 ° C. after addition of the aqueous potassium hydroxide solution was 6.0. . Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 8
(Preparation of Toner H)
A toner was prepared in the same manner as in Example 1 except that in the step (2), a 20 wt% aqueous potassium hydroxide solution was added so that the pH at 25 ° C. after addition of the aqueous potassium hydroxide solution was 5.5. . Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 9
(Preparation of Toner I)
A toner was prepared in the same manner as in Example 1 except that in the step (2), a 20 wt% aqueous potassium hydroxide solution was added so that the pH at 25 ° C. after addition of the aqueous potassium hydroxide solution was 7.4. . Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 10
(Production of Toner J)
Polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (surfactant 1) used in step (1-3) was converted to polyoxyethylene (20) distyrenated phenyl ether monosulfate ammonium salt (surfactant). A toner was prepared in the same manner as in Example 1 except that the procedure was changed to 2). Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 11
(Preparation of toner K)
Polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (surfactant 1) used in step (1-3) was converted to polyoxypropylene (3) polyoxyethylene (10) distyrenated phenyl ether monosulfate A toner was prepared in the same manner as in Example 1 except that the ammonium salt (surfactant 3) was changed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 12
(Preparation of Toner L)
Polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (surfactant 1) used in step (1-3) was converted to polyoxyethylene (10) tribenzylated phenyl ether sulfate ammonium salt (surfactant 4). A toner was prepared in the same manner as in Example 1 except that the above was changed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 13
(Preparation of Toner M)
The polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (surfactant 1) used in the step (1-3) was converted to polyoxyethylene (7) distyrenated (methyl) phenyl ether monosulfate ammonium salt ( A toner was prepared in the same manner as in Example 1 except that the surfactant was changed to 5). Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 14
(Preparation of toner N)
A toner was prepared in the same manner as in Example 1 except that 2.0N sulfuric acid was added so that the pH at 25 ° C. after addition of sulfuric acid was 2.5 in Step (1-3). Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 15
(Production of Toner O)
A toner was prepared in the same manner as in Example 1 except that the step (1-3) was changed as follows. Table 3 shows the physical properties and toner evaluation of the obtained toner.
<Step (1-3): 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 (1-2), an aqueous solution of polyoxyethylene (23) sodium oleyl ether sulfate (anionic surfactant, trade name: Latemule WX, Kao Corporation) ), Solid content 26%) An aqueous solution in which 31.8 g and 8003 g of deionized water were mixed was added. Thereafter, 2.0 N sulfuric acid was added so that the pH at 25 ° C. was 4.5.

Example 16
(Production of Toner P)
The polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (surfactant 1) used in step (1-3) is replaced with polyoxyethylene (13) distyrenated phenyl ether (nonionic surfactant, product). A toner was prepared in the same manner as in Example 1, except that the name was changed to 8.3 g (name: Emulgen A-60, manufactured by Kao Corporation). Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 17
(Production of Toner Q)
The polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (surfactant 1) used in step (1-3) was converted to polyoxyethylene (15) tribenzylphenyl ether (nonionic surfactant, product). A toner was prepared in the same manner as in Example 1 except that the name was changed to Emulgen B-66, manufactured by Kao Corporation. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Example 18
(Preparation of Toner R)
A toner was prepared in the same manner as in Example 1 except that the resin particles added in the step (1-2) were changed to the resin particles (B-2). Table 3 shows the obtained aggregated particles (2), the physical properties of the toner, and the evaluation of the toner.

Example 19
(Production of Toner S)
A toner was prepared in the same manner as in Example 1 except that the 20 wt% potassium hydroxide aqueous solution used in step (2) was changed to triethanolamine. The obtained toner evaluation is shown in Table 3.

Example 20
(Preparation of toner T)
A toner T was produced in the same manner as in Example 1 except that the steps (1-4) and (2) were changed as follows. The obtained toner evaluation is shown in Table 3.
<Step (1-4): Fusion Step of Aggregated Particle (2)>
The dispersion liquid of the aggregated particles (2) whose pH was adjusted in the step (1-3) was heated to 67 ° C. and held at 67 ° C. for 3 hours, and the particles were fused to obtain core-shell particles.
<Step (2): Adjustment of pH of core-shell particle dispersion>
The core-shell particle dispersion obtained in the step (1-4) was cooled to 60 ° C., and a 20 wt% aqueous potassium hydroxide solution was added so that the pH at 25 ° C. was 7.0. Thereafter, the core-shell particle dispersion was held at 60 ° C. with stirring for 1 hour, and then cooled to 25 ° C.

Comparative Example 1
(Preparation of toner U)
A toner was prepared in the same manner as in Example 1 except that the step (2) was not performed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 2
(Preparation of Toner V)
A toner was prepared in the same manner as in Example 1 except that in the step (2), a 20 wt% potassium hydroxide aqueous solution was added so that the pH at 25 ° C. after addition of the potassium hydroxide aqueous solution was 4.5. . Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 3
(Preparation of toner W)
A toner was prepared in the same manner as in Example 1 except that in the step (2), a 20 wt% aqueous potassium hydroxide solution was added so that the pH at 25 ° C. after addition of the aqueous potassium hydroxide solution was 8.0. . Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 4
(Production of Toner X)
A toner was prepared in the same manner as in Example 1 except that in the step (2), a 20 wt% aqueous potassium hydroxide solution was added so that the pH at 25 ° C. after addition of the aqueous potassium hydroxide solution was 8.5. . Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 5
(Preparation of toner Y)
A toner was prepared in the same manner as in Example 10 except that the step (2) was not performed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 6
(Preparation of toner Z)
A toner was prepared in the same manner as in Example 11 except that the step (2) was not performed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 7
(Preparation of Toner A1)
A toner was prepared in the same manner as in Example 12 except that the step (2) was not performed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 8
(Production of Toner B1)
A toner was prepared in the same manner as in Example 13 except that Step (2) was not performed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 9
(Production of Toner C1)
A toner was prepared in the same manner as in Example 15 except that the step (2) was not performed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 10
(Production of Toner D1)
A toner was prepared in the same manner as in Example 16 except that the step (2) was not performed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

Comparative Example 11
(Preparation of Toner E1)
A toner was prepared in the same manner as in Example 1 except that no acid was added in step (1-3) and step (2) was not performed. Table 3 shows the physical properties and toner evaluation of the obtained toner.

  From Table 3, it can be seen that the electrophotographic toners of the examples are all superior in low-temperature fixability, chargeability under high temperature and high humidity, and heat-resistant storage stability as compared with the electrophotographic toners of the comparative examples.

  The electrophotographic toner obtained by the production method of the present invention has both good low-temperature fixability and high-temperature high-humidity chargeability, and excellent heat-resistant storage stability. Therefore, the electrophotographic toner used in electrophotography is used. It can be suitably used as a toner. According to the method of the present invention, a toner having such characteristics can be produced efficiently.

Claims (13)

A method for producing an electrophotographic toner comprising the following steps (1) to (3).
Step (1): After adjusting the pH at 25 ° C. of the aqueous mixed solution containing the aggregated particles including the resin particles (A) and the release agent particles and the surfactant to 2.0 to 5.0 and / or Or a step of fusing the aggregated particles in the aqueous mixed solution while adjusting,
Step (2): Step of adjusting the pH of the fused particle dispersion obtained in Step (1) at 25 ° C. to 5.5 to 7.5 Step (3): Fusion obtained in Step (2) Step of removing toner from particle dispersion to obtain toner particles   2. The electrophotographic toner according to claim 1, wherein the surfactant is an anionic surfactant having a polyalkylene glycol moiety in which an average addition mole number of an alkylene oxide having 2 to 3 carbon atoms is 5 to 100. 3. Production method.   The method for producing an electrophotographic toner according to claim 1 or 2, wherein the resin particles (A) contain a crystalline polyester (a) having a melting point of 60C to 90C. The method for producing an electrophotographic toner according to claim 1, wherein the aggregated particles are aggregated particles (2) obtained by the following steps (1-1) and (1-2).
Step (1-1): Step of obtaining the aggregated particles (1) by mixing the resin particles (A), the release agent particles and the flocculant in an aqueous medium and aggregating them Step (1-2): Step ( Step of adding the resin particles (B) containing the amorphous polyester (b) to the aggregated particles (1) obtained in 1-1) to obtain the aggregated particles (2)   The step of fusing the agglomerated particles maintains the agglomerated particles (2) at a temperature not lower than a temperature 10 ° C lower than the glass transition point of the amorphous polyester (b) and not higher than a temperature 10 ° C higher than the glass transition point. The method for producing an electrophotographic toner according to claim 4, which is a step (1-4) of obtaining fused core-shell particles.   The method for producing an electrophotographic toner according to claim 5, further comprising a step (1-3) of adding the surfactant after the step (1-2) and before the step (1-4).   In step (2), after adjusting the fusion particle dispersion obtained in step (1) to a pH of 25 to 7.5 at 25 ° C., the glass transition point of the resin particles (B) is higher than that. The method for producing an electrophotographic toner according to claim 4, wherein the toner is held at a temperature of 5 ° C. or lower.   The toner for electrophotography according to any one of claims 5 to 7, wherein an acid is added to adjust the pH to 2.0 to 5.0 in the step (1-3) and / or the step (1-4). Manufacturing method. The method for producing an electrophotographic toner according to claim 2, wherein the anionic surfactant is an anionic surfactant represented by the following general formula (1).

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a methyl group, m represents an average value of 1 to 4, and AO represents an ethyleneoxy group. And / or represents a propyleneoxy group, n has an average value of 5 to 100, and M represents ammonium, tetraalkylammonium, or an alkali metal.)   The electron according to any one of claims 1 to 9, wherein in step (2), the pH at 25 ° C of the fused particle dispersion is adjusted to 5.5 to 7.5 using an alkali metal hydroxide. A method for producing a photographic toner.   The method for producing an electrophotographic toner according to claim 5, wherein an average particle diameter of the fused core-shell particles is equal to or less than an average particle diameter of the aggregated particles (2).   The temperature at the time of holding in the step (1-4) is not less than 5 ° C lower than the glass transition point of the resin particles (B) and not more than 10 ° C higher than the glass transition point. The manufacturing method of the toner for electrophotography in any one of -11.   An electrophotographic toner obtained by the production method according to claim 1.