JP7171375B2 - Method for producing toner for electrostatic charge image development - Google Patents

Description

The present invention relates to a method for producing a toner for electrostatic charge image development.

In the field of electrophotography, with the development of electrophotographic systems, there is a demand for the development of electrophotographic toners capable of achieving higher image quality and higher speed. As a method for obtaining a toner that has a narrow particle size distribution, a small particle size, and a fixability that can be used at high speeds, fine resin particles are aggregated and fused in an aqueous medium. A so-called chemical toner is produced by an aggregation fusion method (emulsion aggregation method, aggregation coalescence method) to obtain a toner.

Patent Document 1 describes a process of aggregating polyester-containing resin particles in an aqueous medium to obtain agglomerated particles, a process of flocculating charge control agent particles on the obtained agglomerated particles, and fusing the particles. A method for producing a toner for developing an electrostatic charge image, comprising the step of obtaining toner particles, wherein the volume average particle size of resin particles measured by a light scattering method is 5 nm or more and 50 nm or less. It is said that the charge control agent does not easily detach, there is little fogging during printing, and the transferability during printing is excellent.

In Patent Document 2, wax is added during synthesis of a composite resin containing a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having an alkyl group having 10 to 20 carbon atoms, Alternatively, the composite resin and wax are mixed to obtain a composite resin composition in step 1, an aqueous medium is added to the composite resin composition, phase inversion emulsification is performed, and a shell resin containing the wax and the composite resin is obtained. In step 2 of obtaining an aqueous dispersion (X) of particles, the dispersion (Y) of core resin particles containing a polyester resin (Yp) or a vinyl resin (Yv) is added to the dispersion (Y) obtained in step 2. A method for producing a toner for developing an electrostatic charge image is described, which includes a step 3 of mixing and aggregating an aqueous dispersion (X) to obtain aggregated particles, and a step 4 of fusing the aggregated particles. It is stated that a toner for electrostatic charge image development which is excellent in heat-resistant storage stability, durability and gloss can be obtained.

Patent Document 3 describes a process of obtaining core particles containing a resin and having a volume-median particle size (D ₅₀ ) of 1 to 10 μm in an aqueous medium, and adding a polyester-containing resin and a charged A method for producing a toner is disclosed, which includes a step of adding and adhering fine composite particles containing a control agent to obtain fine composite fine particle-adhered core particles, and a step of heating the obtained fine composite fine particle-adhered core particles to obtain coalesced particles. It is described that the charge control agent can be present on the surface of the toner, an electrophotographic toner having a small particle size and a narrow particle size distribution can be obtained, and the image characteristics are excellent.

JP 2015-118311 A JP 2015-219257 A JP 2012-238022 A

In contrast to the toners of Patent Documents 1 to 3, the speed of electrophotographic systems has recently increased significantly, and therefore toners are required to have further improved low-temperature fixability. On the other hand, it is difficult to obtain a toner for electrostatic image development that exhibits excellent low-temperature fixability and excellent hot offset resistance, and there is a demand for widening the non-offset temperature range.
TECHNICAL FIELD The present invention relates to a method for producing an electrostatic charge image developing toner that exhibits excellent low-temperature fixability and a wide non-offset temperature range.

The present inventors solved the above problems by using a metal complex particle dispersion containing salicylic acid-based metal complex particles having a specific volume-median particle size and a specific particle size distribution when obtaining core particles. is solved, and an electrostatic charge image developing toner having excellent low-temperature fixability and exhibiting a wide non-offset temperature range can be obtained.
The present invention provides a resin particle dispersion containing resin particles X containing an amorphous resin A and a crystalline polyester resin C in the same or different resin particles, and a metal complex particle dispersion containing salicylic acid-based metal complex particles. and aggregating resin particles X and metal complex particles to obtain aggregated particles 1, and attaching resin particles Y containing amorphous polyester resin B to the aggregated particles 1 to obtain aggregated particles 2. , and a step of fusing the aggregated particles 2 in this order, wherein the volume median particle diameter of the salicylic acid-based metal complex particles in the metal complex particle dispersion is 50 nm or more and 250 nm or less, and The present invention relates to a method for producing a toner for electrostatic charge image development, wherein the content of salicylic acid-based metal complex particles having a diameter of 80 nm or less is 20% by volume or less.

According to the present invention, it is possible to provide a method for producing an electrostatic charge image developing toner that exhibits excellent low-temperature fixability and a wide non-offset temperature range.

[Manufacturing Method of Toner for Developing Electrostatic Charge Image]
The method for producing a toner for electrostatic charge image development (hereinafter also simply referred to as "toner") of the present invention contains resin particles X containing an amorphous resin A and a crystalline polyester resin C in the same or different resin particles. a step of mixing a resin particle dispersion and a metal complex particle dispersion containing salicylic acid-based metal complex particles to aggregate the resin particles X and the metal complex particles to obtain aggregated particles 1; a step of obtaining aggregated particles 2 by attaching the resin particles Y containing resin particles Y to the aggregated particles 1, and a step of fusing the aggregated particles 2 in this order, wherein The volume median particle size of the complex particles is 50 nm or more and 250 nm or less, and the content of salicylic acid-based metal complex particles with a particle size of 80 nm or less is 20% by volume or less.
By the above method, a toner for electrostatic charge image development which is excellent in low-temperature fixability and exhibits a wide non-offset temperature range can be obtained.

Although the reason is not clear, it is considered as follows.
The present inventors focused on a method for improving the elasticity of a chemical toner in order to obtain a toner that exhibits excellent low-temperature fixability and a wide non-offset temperature range. As a result, conventional methods such as increasing the molecular weight of the polyester resin or adding a cross-linking agent have problems such as difficulty in producing a resin particle dispersion, and the above problems have been sufficiently solved. it wasn't. On the other hand, the inventors have found that by adding salicylic acid-based metal complex particles in the aggregation step, a toner having excellent low-temperature fixability and exhibiting a wide non-offset temperature range can be obtained. This is because the salicylic acid-based metal complex compound in the salicylic acid-based metal complex particles and the carboxyl groups and ester bonds in the polyester are complexed through coordinate bonding in the toner, thereby improving the elasticity of the toner. presumed to be effective.
In the aqueous medium during chemical toner production, the terminal carboxyl group of the polyester is in a dissociated state, so that it can form a bond with a salicylic acid-based metal complex compound, for example, aluminum, which is the central metal of a salicylic acid aluminum complex. As a result of the metal complex compound acting as a cross-linking agent, it is thought that the elasticity is improved and the effect of widening the non-offset temperature range is exhibited.
That is, in the present invention, it was found that the addition of a salicylic acid-based metal complex compound has the effect of widening the non-offset temperature range.
Furthermore, the present inventors have found that it is very important to adjust the particle size of the salicylic acid-based metal complex particles to a specific range in order to introduce the salicylic acid-based metal complex compound into the toner so as to obtain such effects. found to be important. That is, in order to efficiently combine the polyester in the toner with the salicylic acid-based metal complex compound in the salicylic acid-based metal complex particles, a metal complex particle dispersion liquid in which the salicylic acid-based metal complex particles are finely dispersed in advance is prepared. It is important to use This is because the salicylic acid-based metal complex particles are insoluble in water. On the other hand, if the salicylic acid-based metal complex particles are finely dispersed excessively, the complex structure of the salicylic acid metal complex compound in the salicylic acid-based metal complex particles is considered to collapse. As a result, the polyvalent metal, which is the central metal of the salicylic acid-based metal complex compound, tends to be liberated, and excessive aggregates are likely to occur. As it deteriorates, the appropriate effect of expanding the non-offset temperature range due to the increase in elasticity cannot be obtained.
For this reason, the present inventors obtained good low-temperature fixability and a wide non-offset temperature range by aggregating and fusing finely dispersed salicylic acid-based metal complex particles together with resin particles. have found that salicylic acid-based metal complex particles having a specific range of are important.

Definitions of various terms used in this specification are shown below.
Whether a resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (°C)/maximum endothermic peak temperature (°C)) in the measurement method described in the Examples below. A crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins are those having a crystallinity index of less than 0.6 or greater than 1.4. The crystallinity index can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate.
In the specification, the carboxylic acid component of the polyester resin includes not only the compound but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of each carboxylic acid (the number of carbon atoms in the alkyl group is 1 or more and 3 or less). is also included.
"Volume-median particle size ( _D50 )" is a particle size at which the cumulative volume frequency calculated as a volume fraction is 50%, calculated from the smaller particle size.
The coefficient of variation of particle size distribution (hereinafter also simply referred to as “CV value”) is a value represented by the following formula. The volume average particle size in the following formula is the particle size obtained by multiplying the particle size measured on a volume basis by the ratio of particles having that particle size value, and dividing the resulting value by the number of particles. be.
CV value (%) = [standard deviation of particle size distribution (μm)/volume average particle size (μm)] × 100

A method for producing a toner according to one embodiment of the present invention includes, for example, a resin particle dispersion containing resin particles X containing an amorphous resin A and a crystalline polyester resin C in the same or different resin particles; a step of mixing with a metal complex particle dispersion containing complex particles to aggregate resin particles X and metal complex particles to obtain aggregated particles 1 (hereinafter also referred to as “step (1)”);
A step of attaching resin particles Y containing an amorphous polyester resin B to the aggregated particles 1 to obtain aggregated particles 2 (hereinafter also referred to as “step (2)”), and fusing the aggregated particles 2 (hereinafter also referred to as “step (3)”) in this order.
The present invention will be described below by taking the embodiment as an example.

<Step (1)>
[Resin particle dispersion]
The resin particle dispersion used in step 1 contains resin particles X. The resin particles X contain the amorphous resin A and the crystalline polyester resin C in the same or different resin particles in order to obtain excellent low-temperature fixability. From the viewpoint of broadening the range, the amorphous resin A and the crystalline polyester resin C are preferably included in the same resin particles.

<<Amorphous resin A>>
Amorphous resin A is, for example, an amorphous polyester resin that is a polycondensate of an alcohol component and a carboxylic acid component.
Examples of amorphous polyester resins include polyester resins and modified polyester resins. Modified polyester resins include, for example, urethane-modified polyester resins, epoxy-modified polyester resins, and composite resins containing polyester resin segments and vinyl resin segments. Among these, it is an amorphous resin containing a polyester resin segment that is a polycondensate of an alcohol component and a carboxylic acid component and an addition polymerized resin segment that is an addition polymer of a raw material monomer containing a styrene compound. preferable.

Examples of the alcohol component include alkylene oxide adducts of aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, alkylene oxide adducts of aromatic diols are preferable from the viewpoint of obtaining a toner excellent in low-temperature fixability.
The alkylene oxide adduct of an aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

（式中、ＯＲ^１及びＲ^２Ｏはオキシアルキレン基であり、Ｒ^１及びＲ^２はそれぞれ独立にエチレン基又はプロピレン基であり、ｘ及びｙはアルキレンオキシドの平均付加モル数を示し、それぞれ正の数であり、ｘとｙの和の値は、１以上、好ましくは１．５以上であり、１６以下、好ましくは８以下、より好ましくは４以下である）で表されるビスフェノールＡのアルキレンオキシド付加物である。

(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y represent the average number of moles of alkylene oxide added, each positive and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less). It is an oxide adduct.

The alkylene oxide adducts of bisphenol A include, for example, propylene oxide adducts of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] and ethylene oxide adducts of bisphenol A. These may use 1 type(s) or 2 or more types. Among these, the propylene oxide adduct of bisphenol A is preferred.
The content of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, Even more preferably, it is 100 mol %.

Examples of linear or branched aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 1,4-butanediol. , 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 12-dodecanediol.
Examples of alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane], alkylene oxide adducts of hydrogenated bisphenol A having 2 to 4 carbon atoms (average number of added moles: 2 above and below 12).
Examples of trihydric or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
One or more of these alcohol components may be used.

Examples of the carboxylic acid component include dicarboxylic acids and polycarboxylic acids having a valence of 3 or more.
Dicarboxylic acids include, for example, aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferred.
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, and preferably It is 90 mol % or less, more preferably 85 mol % or less, still more preferably 80 mol % or less.

The number of carbon atoms in the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Linear or branched aliphatic dicarboxylic acids include, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, and azelaic acid. , and succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Examples of the succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include dodecylsuccinic acid, dodecenylsuccinic acid, and octenylsuccinic acid. Among these, fumaric acid, sebacic acid, and succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms are preferred.
The amount of linear or branched aliphatic dicarboxylic acid in the carboxylic acid component is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 80 mol%. Below, more preferably 50 mol % or less, still more preferably 30 mol % or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, such as trimellitic acid. Preferred is trimellitic acid or its anhydride.
When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, and still more preferably 8 mol% in the carboxylic acid component. and preferably 30 mol % or less, more preferably 25 mol % or less, still more preferably 20 mol % or less.
One or more of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group/OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.

The addition polymerized resin segment is, for example, an addition polymer of raw material monomers containing styrene compounds.
Styrenic compounds include, for example, unsubstituted or substituted styrene. Examples of the substituent with which styrene is substituted include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group, or a salt thereof.
Styrenic compounds include, for example, styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts thereof. Among these, styrene is preferred.
The content of the styrenic compound in the raw material monomers of the addition polymerized resin segment is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 75% by mass or more, and 100% by mass or less. , preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

Examples of raw material monomers other than styrene compounds include (meth)acrylic acid esters such as alkyl (meth)acrylate, benzyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate; olefins; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; . Among these, (meth)acrylic acid esters are preferred, and alkyl (meth)acrylates are more preferred.
The number of carbon atoms in the alkyl group in the alkyl (meth)acrylate is preferably 1 or more, more preferably 6 or more, still more preferably 10 or more, and is preferably 24 or less, more preferably 22 or less, and still more preferably 20. It is below.
Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, (iso- or tertiary) butyl (meth)acrylate, (meth)acrylate, ) (iso)amyl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, (meth)acrylic acid ( iso) dodecyl, (iso) palmityl (meth) acrylate, (iso) stearyl (meth) acrylate, (iso) behenyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate or (meth) Stearyl acrylate is preferred, and stearyl (meth)acrylate is more preferred.
In addition, "(iso or tertiary)" and "(iso)" mean both when these prefixes exist and when they do not exist, and when these prefixes do not exist, normal is indicated. Moreover, "(meth)acrylic acid" indicates acrylic acid or methacrylic acid.

The (meth)acrylic acid ester content in the raw material monomers of the addition polymerized resin segment is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or more. % by mass or less, more preferably 35% by mass or less, and even more preferably 25% by mass or less.
The total amount of the styrenic compound and the (meth)acrylic acid ester in the raw material monomers of the addition polymerized resin segment is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably. is 100% by mass.

Amorphous resin A preferably has structural units derived from bi-reactive monomers that are covalently bonded to polyester resin segments and addition polymerized resin segments.
The “structural unit derived from a bireactive monomer” means a unit obtained by reacting a functional group and an addition polymerizable group of a bireactive monomer.
Examples of addition polymerizable groups include carbon-carbon unsaturated bonds (ethylenically unsaturated bonds).
The bi-reactive monomers include, for example, addition polymerizable monomers having at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule. . Among these, addition polymerizable monomers having at least one functional group selected from a hydroxyl group and a carboxy group are preferred, and addition polymerizable monomers having a carboxy group are more preferred, from the viewpoint of reactivity.
Addition-polymerizable monomers having a carboxy group include, for example, acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred, from the viewpoint of reactivity in both polycondensation reaction and addition polymerization reaction.
When the bireactive monomer is an addition-polymerizable monomer having a carboxy group, the amount of the structural unit derived from the bireactive monomer is preferably It is 1 mol part or more, more preferably 5 mol parts or more, still more preferably 8 mol parts or more, and preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less.

The content of the polyester resin segment in the amorphous resin A is preferably 35% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and preferably 90% by mass or less, and more It is preferably 85% by mass or less, more preferably 75% by mass or less.

The content of the addition polymerized resin segment in the amorphous resin A is preferably 5% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and preferably 60% by mass or less, More preferably 55% by mass or less, still more preferably 45% by mass or less.

The amount of the structural unit derived from the bi-reactive monomer in the amorphous resin A is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more, The content is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

The total amount of the polyester resin segment, the addition polymerization resin segment, and the structural units derived from the bireactive monomer in the amorphous resin A is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass. or more, and not more than 100% by mass, and even more preferably 100% by mass.

Amorphous resin A may be produced, for example, by a method comprising step A of polycondensing an alcohol component and a carboxylic acid component, and step B of addition polymerizing a raw material monomer of an addition polymerized resin segment and a bi-reactive monomer. good.
Process B may be performed after process A, process A may be performed after process B, or process A and process B may be performed simultaneously.
In step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, and then step B is performed, and then the remainder of the carboxylic acid component is added to the polymerization system to perform the polycondensation reaction of step A and, if necessary, both reactions. A method of further advancing the reaction with the organic monomer is preferred.

In step A, an esterification catalyst such as di(2-ethylhexanoic acid)tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamine, etc. is added to the alcohol component and the carboxylic acid component in a total amount of 100, if necessary. 0.01 parts by mass or more and 5 parts by mass or less per part by mass; Esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid), total amount of alcohol component and carboxylic acid component is 100 mass 0.001 parts by mass or more and 0.5 parts by mass or less may be used for polycondensation.
Further, when a monomer having an unsaturated bond such as fumaric acid is used for polycondensation, it is preferably 0.001 part by mass or more with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component, if necessary. A radical polymerization inhibitor of 0.5 parts by mass or less may be used. Examples of radical polymerization inhibitors include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

Examples of the radical polymerization initiator for addition polymerization in step B include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and 2,2′-azobis(2,4-dimethylvaleronitrile) such as azo compounds.
The amount of the radical polymerization initiator to be used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer for the addition polymerization resin segment.
The addition polymerization temperature is preferably 110° C. or higher, more preferably 130° C. or higher, and preferably 230° C. or lower, more preferably 220° C. or lower, still more preferably 210° C. or lower.

(Physical properties of amorphous resin A)
The softening point of the amorphous resin A is preferably 70° C. or higher, more preferably 90° C. or higher, and still more preferably 100° C. or higher. It is more preferably 140° C. or lower, still more preferably 125° C. or lower.
The glass transition temperature of the amorphous resin A is preferably 30° C. or higher, more preferably 35° C. or higher, and still more preferably 40° C. or higher, and is preferably 80° C. or lower from the viewpoint of further improving low-temperature fixability. , more preferably 70° C. or lower, still more preferably 60° C. or lower.

The acid value of the amorphous resin A is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g. Below, more preferably 30 mgKOH/g or less.
The softening point, glass transition temperature, and acid value of the amorphous resin A can be appropriately adjusted depending on the type and amount of raw material monomers used, and production conditions such as reaction temperature, reaction time, and cooling rate. Those values are determined by the method described in Examples.
When two or more amorphous resins A are used in combination, it is preferable that the softening point, glass transition temperature and acid value of the mixture are within the ranges described above.

The content of the amorphous resin A is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more, relative to the total amount of the resin components of the resin particles X, and It is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, still more preferably 80% by mass or less, and even more preferably 75% by mass or less.

<<Crystalline polyester resin C>>
Crystalline polyester resin C is a polycondensate of an alcohol component and a carboxylic acid component.
As the alcohol component, α,ω-aliphatic diols are preferred.
The number of carbon atoms in the α,ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. be.
Examples of α,ω-aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol mentioned. Among these, 1,6-hexanediol, 1,10-decanediol and 1,12-dodecanediol are preferred, and 1,10-decanediol is more preferred.

The amount of the α,ω-aliphatic diol in the alcohol component is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol % or less, more preferably 100 mol %.

The alcohol component may contain other alcohol components different from the α,ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α,ω-aliphatic diols such as 1,2-propanediol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; Trihydric or higher alcohols such as erythritol and trimethylolpropane are included. One or more of these alcohol components may be used.

As the carboxylic acid component, aliphatic dicarboxylic acids are preferable, and linear aliphatic dicarboxylic acids are more preferable.
The number of carbon atoms in the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Aliphatic dicarboxylic acids include, for example, fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid and dodecanedioic acid are preferred, and sebacic acid is more preferred. One or more of these carboxylic acid components may be used.

The amount of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol % or less, more preferably 100 mol %.

The carboxylic acid component may contain other carboxylic acid components different from the aliphatic dicarboxylic acid. Other carboxylic acid components include, for example, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and trivalent or higher polyvalent carboxylic acids. One or more of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group/OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.

Examples of the method for producing the crystalline polyester resin C include the same examples as the step A for the amorphous resin A described above.

(Physical properties of crystalline polyester resin C)
The softening point of the crystalline polyester resin C is preferably 60° C. or higher, more preferably 70° C. or higher, and still more preferably 80° C. or higher, from the viewpoint of toner storage stability, and from the viewpoint of further improving low-temperature fixability. Therefore, the temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and still more preferably 100° C. or lower.
The melting point of the crystalline polyester resin C is preferably 50° C. or higher, more preferably 60° C. or higher, and still more preferably 70° C. or higher from the viewpoint of toner storage stability, and from the viewpoint of further improving low-temperature fixability. , preferably 100° C. or lower, more preferably 90° C. or lower, and still more preferably 80° C. or lower.

The acid value of the crystalline polyester resin C is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and preferably 35 mgKOH/g or less, more preferably 25 mgKOH/g or less, still more preferably 20 mgKOH/g. It is below.
The softening point, melting point, and acid value of the crystalline polyester resin C can be appropriately adjusted depending on the type and amount of the raw material monomer used, and the production conditions such as the reaction temperature, reaction time, and cooling rate. It is obtained by the method described in . When two or more crystalline polyester resins C are used in combination, the softening point, melting point, and acid value obtained as a mixture thereof are preferably within the above ranges.

Dispersion can be carried out using a known method, but it is preferable to disperse by a phase inversion emulsification method. The phase inversion emulsification method includes, for example, a method in which an aqueous medium is added to an organic solvent solution of a resin or a molten resin to effect phase inversion emulsification.

The organic solvent used for phase inversion emulsification is not particularly limited as long as it dissolves the resin, but from the viewpoint of facilitating phase inversion, for example, alcoholic solvents such as ethanol, isopropanol, and isobutanol; acetone, methyl ethyl ketone, and methyl isobutyl ketone. , diethyl ketone and the like; ether solvents such as dibutyl ether, tetrahydrofuran and dioxane; and acetate solvents such as ethyl acetate and isopropyl acetate. Among these, ketone-based solvents and acetic acid ester-based solvents are preferable, and methyl ethyl ketone, ethyl acetate, and isopropyl acetate are more preferable, from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium.
A neutralizing agent is preferably added to the organic solvent solution. Neutralizing agents include, for example, basic substances. Basic substances include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The use equivalent (mol%) of the neutralizing agent to the acid groups of the resin contained in the resin particles X is preferably 10 mol% or more, more preferably 10 mol% or more, from the viewpoint of obtaining fine resin particles and improving the dispersion stability. It is preferably 30 mol % or more, more preferably 40 mol % or more, and preferably 90 mol % or less, more preferably 70 mol % or less.
The equivalent amount (mol%) of the neutralizing agent to be used can be determined by the following formula. The use equivalent of the neutralizing agent is synonymous with the degree of neutralization when it is 100 mol % or less.
Equivalent amount of neutralizing agent used (mol%) = [{added mass of neutralizing agent (g)/equivalent amount of neutralizing agent}/[{weighted average acid value of resin constituting resin particles X (mgKOH/g) x Mass (g) of resin constituting resin particles X}/(56×1000)]]×100

While stirring the organic solvent solution or molten resin, the aqueous medium is gradually added to cause phase inversion.
From the viewpoint of improving the dispersion stability of the resin particles X, the temperature of the organic solvent solution when adding the aqueous medium is preferably at least the glass transition temperature of the resin constituting the resin particles X, more preferably at least 50° C., even more preferably at least 50° C. is 60° C. or higher, and preferably 85° C. or lower, more preferably 80° C. or lower.
The contents of the amorphous resin A and the crystalline polyester resin C are as described above.

After the phase inversion emulsification, if necessary, the organic solvent may be removed from the resulting dispersion by distillation or the like. In this case, the residual amount of the organic solvent in the dispersion is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably substantially 0% by mass.

The volume-median particle size (D ₅₀ ) of the resin particles X in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, from the viewpoint of obtaining a toner capable of obtaining high-quality images, and , preferably 0.8 μm or less, more preferably 0.4 μm or less, and still more preferably 0.3 μm or less.
The CV value of the resin particles X in the dispersion liquid is preferably 10% or more, more preferably 20% or more, and more preferably 40% or less, more preferably from the viewpoint of obtaining a toner capable of obtaining high-quality images. is 35% or less, more preferably 30% or less.
The volume-median particle size ( _D50 ) and CV value of the resin particles are obtained by the methods described in Examples below.

When the resin particles Xa containing the amorphous resin A and the resin particles Xc containing the crystalline polyester resin C are mixed and used, the resin particles Xa and Xc can be obtained by the same method as described above.
The amount of the resin particles Xa and the resin particles Xc to be added is preferably the amount corresponding to the content of the amorphous resin A and the crystalline polyester resin C described above.

[Metal complex particle dispersion]
The metal complex particle dispersion contains salicylic acid-based metal complex particles.
<<Salicylic acid-based metal complex compound>>
From the viewpoint of obtaining a toner having a wider non-offset temperature range, the salicylic acid-based metal complex compound is preferably an alkylsalicylic acid metal complex compound represented by the following formula (1).

式（１）中、Ｒ^１及びＲ^２はそれぞれ独立に、炭素数１以上８以下のアルキル基を示し、Ｍは、アルミニウム、鉄、亜鉛又はクロムを示す。

In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, and M represents aluminum, iron, zinc or chromium.

In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear, branched or cyclic. And from the viewpoint of the stability of the complex, it is preferably a linear or branched alkyl group, more preferably a branched alkyl group. From the viewpoint of availability, R ¹ and R ² are preferably alkyl groups having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert -Butyl group is exemplified, and among these, tert-butyl group is preferable from the viewpoint of availability and stability of the complex.
Further, although the substitution positions of R ¹ and R ² are not particularly limited, substitution at the 3-position and the 5-position is preferred.

M represents aluminum, iron, zinc or chromium, preferably aluminum, iron or zinc, more preferably aluminum from the viewpoint of the stability of the complex and environmental safety.

As the salicylic acid-based metal complex compound, commercially available products may be used, and commercially available products include "BONTRON (registered trademark) E-84", "BONTRON (registered trademark) E-304" ( Central metal: zinc); "BONTRON (registered trademark) E-88", "BONTRON (registered trademark) E-108" (central metal: aluminum); "BONTRON (registered trademark) X-11" (central metal: iron) "BONTRON (registered trademark) E-81" (central metal: chromium), (manufactured by Orient Chemical Industry Co., Ltd.), and the like.

From the viewpoint of obtaining a toner having a wide non-offset temperature range, the amount of the salicylic acid-based metal complex compound added to the toner is preferably 0.3 parts by mass or more with respect to 100 parts by mass of the total amount of all resin components in the toner. , more preferably 0.4 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 2.5 parts by mass or less, more preferably 2.2 parts by mass or less, still more preferably 2.0 Part by mass or less.

(Salicylic acid-based metal complex particle dispersion)
The salicylic acid-based metal complex compound is contained in the aggregated particles 1 by mixing the salicylic acid-based metal complex particle dispersion with the resin particle dispersion and causing aggregation.
The volume-median particle size ( _D50 ) of the salicylic acid-based metal complex particles is 50 nm or more, preferably 80 nm or more, more preferably 100 nm or more, and 250 nm or less, from the viewpoint of obtaining a toner having a wide non-offset temperature. , preferably 200 nm or less, more preferably 180 nm or less.
When the volume-median particle size of the salicylic acid-based metal complex particles is within the above range, the dispersibility in the aggregated particles 1 is improved, so that the dispersibility of the salicylic acid-based metal complex particles is improved in the obtained toner, and the particles are efficiently dispersed. It acts as a cross-linking agent, resulting in a wider non-offset temperature range of the toner.

In addition, the content of salicylic acid-based metal complex particles having a particle size of 80 nm or less among the salicylic acid-based metal complex particles is 20% by volume or less from the viewpoint of obtaining a toner having a wide non-offset temperature. By setting the content of the salicylic acid-based metal complex particles having a particle diameter of 80 nm or less within the above range, destruction of the complex structure of the salicylic acid-based metal complex compound in the salicylic acid-based metal complex particles is suppressed, and a wide non-offset temperature range is achieved. A toner having
The content of salicylic acid-based metal complex particles having a particle size of 80 nm or less is preferably 15% by volume or less, more preferably 10% by volume or less, even more preferably 8% by volume or less, and even more preferably 5% by volume or less. The preferable lower limit of the content of salicylic acid-based metal complex particles having a particle size of 80 nm or less is not particularly limited, but from the viewpoint of ease of production, it is preferably 0.1% by volume or more, more preferably 0.3% by volume or more, and further Preferably, it is 0.5% by volume or more.

The CV value of the salicylic acid-based metal complex particles enhances the ease of production, the dispersion stability in the metal complex particle dispersion, and the uniformity of the salicylic acid-based metal complex particles in the toner, and has a wider non-offset temperature range. From the viewpoint of obtaining a toner, it is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and preferably 45% or less, more preferably 40% or less, further preferably 38% or less. be.

The metal complex particle dispersion liquid is preferably a dispersion liquid in which a salicylic acid-based metal complex compound is dispersed in an aqueous medium.
The content of the salicylic acid-based metal complex particles in the metal complex particles is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, from the viewpoint of obtaining a toner having a wide non-offset temperature range. , more preferably 98% by mass or more, more preferably substantially 100% by mass, still more preferably 100% by mass.
The solid content concentration (content) of the metal complex particle dispersion is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, from the viewpoint of dispersion stability of the salicylic acid-based metal complex particles. and is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.

From the viewpoint of the dispersion stability of the metal complex particles, a dispersant may be used when dispersing them in the aqueous medium, and it is preferable to use a dispersant.
As the dispersant, surfactants are preferred. Examples of surfactants include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; Ionic surfactants are exemplified. Among these, from the viewpoint of dispersion stability of salicylic acid-based metal complex particles, anionic surfactants are preferred, alkylbenzenesulfonates are more preferred, and linear alkylbenzenesulfonates are even more preferred.
The amount of the dispersant to be added is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more with respect to 100 parts by mass of the metal complex particles, from the viewpoint of dispersion stability. The content is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.

As a method for dispersing the metal complex particle dispersion liquid in the aqueous medium, it is preferable to use a known dispersing machine. Examples of dispersers include homogenizers, high-pressure dispersers, ultrasonic dispersers, and bead mills. It may be appropriately selected and used so as to obtain the desired particle size distribution described above.

In the present invention, the pH of the metal complex particle dispersion is preferably 6 or more and 8 or less. In the metal complex particle dispersion liquid, the salicylic acid-based metal complex compound is dispersed in the aqueous medium. Excessive dispersion decomposes the complex structure of the salicylic acid-based metal complex, and the pH of the metal complex particle dispersion liquid is lowered. tend to decline. Therefore, in order to keep the content of the salicylic acid-based metal complex particles of 80 nm or less within the above range, it is preferable to perform a dispersion treatment so that the metal complex particle dispersion liquid has a pH of 6 or more.

[Mixing conditions]
In step (1), resin particle dispersion containing resin particles X containing amorphous resin A and crystalline polyester resin C in the same or different resin particles, and metal complex particle dispersion containing salicylic acid-based metal complex particles The resin particles X and the metal complex particles are aggregated to obtain the aggregated particles 1 by mixing with the liquid. When the aggregated particles 1 contain salicylic acid-based metal complex particles having a specific particle size distribution, it is possible to obtain an electrostatic charge image developing toner having excellent low-temperature fixability and a wide non-offset temperature range.
In step (1), if necessary, release agent particles and colorant particles can be aggregated together with resin particles X and metal complex particles.

≪Release agent≫
In step (1), release agent particles containing a release agent may be aggregated together with the resin particles X and the metal complex particles.
Release agents include, for example, polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sasol wax; and oxides thereof; carnauba wax. , montan waxes or their deoxidized waxes, ester waxes such as fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. These may use 1 type(s) or 2 or more types.

The melting point of the releasing agent is preferably 60° C. or higher, more preferably 70° C. or higher, and preferably 160° C. or lower, more preferably 150° C. or lower, and still more preferably 140° C. or lower.
The content of the release agent in the toner is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably It is 15% by mass or less.

(Dispersion of Release Agent Particles)
The release agent is preferably contained in the aggregated particles 1 by mixing the release agent particle dispersion with the resin particle dispersion and the metal complex particle dispersion and causing aggregation.
Although a dispersion of release agent particles can be obtained using a surfactant, it is preferably obtained by mixing the release agent with resin particles Z described later. By preparing release agent particles using a release agent and resin particles Z, the release agent particles are stabilized by the resin particles Z, and the release agent can be dispersed in an aqueous medium without using a surfactant. Dispersion becomes possible. It is considered that the dispersion liquid of release agent particles has a structure in which a large number of resin particles Z adhere to the surface of the release agent particles.

The resin constituting the resin particles Z in which the release agent is dispersed is preferably a polyester-based resin, and it is more preferable to use a composite resin D having a polyester resin segment and an addition polymerized resin segment.

The softening point of composite resin D is preferably 70° C. or higher, more preferably 80° C. or higher, and preferably 140° C. or lower, more preferably 120° C. or lower, and still more preferably 100° C. or lower.
The acid value of Composite Resin D is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g, from the viewpoint of obtaining fine resin particles and obtaining a fine releasing agent particle dispersion. Above, more preferably 20 mgKOH/g or more, preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, still more preferably 30 mgKOH/g or less.

Other suitable ranges of resin properties of Composite Resin D, suitable examples of raw material monomers constituting the resin, and the like are the same as those shown for Amorphous Resin A. A dispersion of the resin particles Z can be obtained, for example, by the above-described phase inversion emulsification method.
The volume-median particle size (D ₅₀ ) of the resin particles Z is preferably 0.01 μm or more, more preferably 0.03 μm or more, and preferably 0.01 μm or more, from the viewpoint of the dispersion stability of the release agent particles. It is 3 μm or less, more preferably 0.2 μm or less.
From the viewpoint of the dispersion stability of the release agent particles, the CV value of the resin particles Z is preferably 10% or more, more preferably 15% or more, and preferably 40% or less, more preferably 35% or less. More preferably, it is 30% or less.

The release agent particle dispersion is prepared, for example, by dispersing the release agent, the resin particle dispersion, and, if necessary, an aqueous medium at a temperature equal to or higher than the melting point of the release agent using a homogenizer, a high-pressure disperser, an ultrasonic disperser, or the like. Obtained by dispersing using a disperser.
The heating temperature during dispersion is preferably the melting point of the release agent or higher and 80° C. or higher, more preferably 85° C. or higher, still more preferably 90° C. or higher, and preferably softens the resin contained in the resin particles Z. It is less than 10°C higher than the point and 100°C or less, more preferably 98°C or less, still more preferably 95°C or less.

The amount of resin particles Z is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and preferably 100 parts by mass or less with respect to 100 parts by mass of the release agent. , more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less.

The volume median particle size ( _D50 ) of the release agent particles is preferably 0.05 µm or more, more preferably 0.2 µm or more, and still more preferably 0.4 µm or more, from the viewpoint of obtaining uniform aggregated particles by aggregation. Yes, and preferably 1 μm or less, more preferably 0.8 μm or less, and even more preferably 0.6 μm or less.
The CV value of the release agent particles is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably 35% or less, still more preferably 30% or less.
The volume-median particle diameter ( _D50 ) and CV value of the release agent particles are measured according to the methods described in Examples.

≪Colorant≫
In the step (1), together with the resin particles X, colorant particles containing a colorant may be aggregated.
As the colorant, all dyes, pigments, etc. used as colorants for toners can be used.
Examples of colorants include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, and disazo yellow. be done. The toner may be black toner or color toner other than black.

From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass, with respect to the total of 100 parts by mass of the amorphous resin A and the crystalline polyester resin C. Above, more preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

(Dispersion of colorant particles)
The colorant is preferably contained in the aggregated particles 1 by mixing the resin particles X and the metal complex particles as a dispersion liquid of the colorant particles and causing them to aggregate.
The dispersion liquid of the colorant particles is preferably obtained by dispersing the colorant and the aqueous medium using a dispersing machine such as a homogenizer or an ultrasonic dispersing machine. From the viewpoint of improving the dispersion stability of the colorant, the dispersion is preferably carried out in the presence of a surfactant. Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. From the viewpoint of improving the dispersion stability of colorant particles, anionic surfactants are preferred. is an agent. Anionic surfactants include, for example, dodecyl benzene sulfonate, dodecyl sulfate, lauryl ether sulfate, and alkenyl succinate. Among these, dodecylbenzenesulfonate is preferred.

From the viewpoint of improving the dispersion stability of the colorant, the content of the surfactant in the dispersion of the colorant particles is preferably 1 part by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the colorant. Above, more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

The volume median particle diameter ( _D50 ) of the colorant particles is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.1 μm or more, and preferably 0.3 μm or less, more preferably 0.1 μm or more. It is preferably 0.2 μm or less.
The method for measuring the volume-median particle size ( _D50 ) of the colorant particles is according to the method described in Examples.

Agglomerated particles 1 also contain charge control agents other than salicylic acid-based metal complex compounds, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleanability. Additives such as improvers may also be included.

≪Surfactant≫
In the step (1), it is preferable to coagulate the resin particles X and the metal complex particles after preparing a mixed dispersion by mixing at least the resin particle dispersion and the metal complex particle dispersion.
When preparing a mixed dispersion, from the viewpoint of improving the dispersion stability of optional components such as resin particles X, metal complex particles, and optionally added release agent particles and colorant particles, a surfactant is added. may be performed in the presence of Examples of surfactants include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers. One or more surfactants may be used.
When a surfactant is used, the amount used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the resin particles X. parts or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.

Mixing of the dispersion liquid of the resin particles X, the dispersion liquid of the metal complex particles, and the optional components is carried out by a conventional method. From the viewpoint of efficient aggregation, it is preferable to add a flocculant to the mixed dispersion obtained by the mixing.

Examples of flocculants include cationic surfactants of quaternary salts, organic flocculants such as polyethyleneimine; inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride, calcium nitrate; ammonium sulfate, chloride inorganic ammonium salts such as ammonium and ammonium nitrate; and inorganic flocculants such as bivalent or higher metal complexes. From the viewpoint of improving cohesiveness and obtaining uniform aggregated particles, a monovalent to pentavalent inorganic flocculant is preferable, a monovalent to divalent inorganic metal salt and inorganic ammonium salt are more preferable, and ammonium sulfate is even more preferable. . Although the flocculant may be added as it is, it is preferable to dissolve it in an aqueous medium and add it as an aqueous solution. Moreover, when adding a flocculant as aqueous solution, you may adjust pH of flocculant aqueous solution.

Using an aggregating agent, for example, 5 parts by mass or more and 50 parts by mass or less of an aggregating agent is added to a mixed dispersion containing resin particles X and metal complex particles at 0° C. or higher and 40° C. or lower with respect to 100 parts by mass of resin particles X. Then, the resin particles X and the metal complex particles are aggregated in an aqueous medium to obtain aggregated particles 1 . Furthermore, from the viewpoint of promoting aggregation, it is preferable to raise the temperature of the dispersion after adding the aggregating agent.

The volume-median particle size (D ₅₀ ) of aggregated particles 1 is preferably 2 µm or more, more preferably 3 µm or more, still more preferably 4 µm or more, and preferably 10 µm or less, more preferably 8 µm or less, and still more preferably 6 μm or less. The volume-median particle size (D ₅₀ ) of Aggregated Particles 1 is determined by the method described in Examples below.

<Step (2)>
In step (2), resin particles Y containing amorphous polyester resin B are attached to aggregated particles 1 to obtain aggregated particles 2 .
[Resin Particle Y]
The dispersion liquid of the resin particles Y is obtained by the same method as the method for producing the dispersion liquid of the resin particles X described above.
In step (2), for example, by adding a dispersion liquid of resin particles Y to a dispersion liquid containing aggregated particles 1 at 30° C. or higher and 80° C. or lower, resin particles Y are attached to aggregated particles 1 in an aqueous medium. , to obtain agglomerated particles 2.

<<Amorphous polyester resin B>>
Examples of the amorphous polyester-based resin B include polyester resins and composite resins containing polyester resin segments and addition polymerized resin segments. Among these, polyester resins, which are polycondensates of alcohol components and carboxylic acid components, are preferred.

When the amorphous polyester-based resin B is a polyester resin, the alcohol component and the carboxylic acid component are the same as the examples of the polyester resin segment in the amorphous resin A described above. In the case of a composite resin, examples of the amorphous polyester-based resin B are the same as those of the amorphous resin A described above.
Preferred embodiments of the polyester-based resin B will be described below, omitting common examples. In a preferred embodiment, a toner having excellent low-temperature fixability can be obtained.
The alcohol component is preferably an alkylene oxide adduct of an aromatic diol, more preferably an alkylene oxide adduct of bisphenol A, still more preferably an alkylene oxide adduct of bisphenol A represented by formula (I). . As the alkylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol A is preferred.
The content of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, More preferably, it is 100 mol %.

Examples of the method for producing the amorphous polyester-based resin B include the same examples as the step A for the amorphous resin A described above.

(Physical properties of amorphous polyester resin B)
The softening point of the amorphous polyester resin B is preferably 70° C. or higher, more preferably 90° C. or higher, and still more preferably 100° C. or higher. Below, more preferably 130° C. or less, and still more preferably 125° C. or less.
The glass transition temperature of the amorphous polyester resin B is preferably 30° C. or higher, more preferably 40° C. or higher, and still more preferably 50° C. or higher. °C or less, more preferably 75°C or less, and even more preferably 70°C or less.

The acid value of the amorphous polyester-based resin B is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, from the viewpoint of further improving the charging performance maintenance rate, and It is preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, still more preferably 30 mgKOH/g or less.
The softening point, glass transition temperature, and acid value of the amorphous polyester-based resin B can be appropriately adjusted depending on the type and amount of raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate. Moreover, those values are determined by the method described in Examples.
When two or more amorphous polyester resins B are used in combination, the softening point, glass transition temperature and acid value obtained as a mixture thereof are preferably within the ranges described above.

Resin particles Y containing amorphous polyester-based resin B can be obtained, for example, by the same method as resin particles X described above.

The content of the amorphous polyester resin B is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably, based on the total amount of the resin components of the resin particles Y. is 95 mass % or more and 100 mass % or less, more preferably 100 mass %.
Mass ratio of amorphous polyester resin B to the total amount of amorphous resin A and crystalline polyester resin C [amorphous polyester resin B / total amount of amorphous resin A and crystalline polyester resin C ] is preferably 5/95 or more, more preferably 10/90 or more, still more preferably 15/85 or more, and is preferably 30/70 or less, more preferably 25/75 or less, still more preferably 20/ 80 or less.

The aggregation may be stopped when the aggregated particles 2 have grown to a particle size suitable for toner particles.
Methods for stopping aggregation include, for example, a method of cooling the dispersion, a method of adding an aggregation inhibitor, a method of diluting the dispersion, and a method of changing the pH. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation terminator is preferred.

[Aggregation terminating agent]
As the aggregation terminator, a surfactant is preferred, and an anionic surfactant is more preferred. Anionic surfactants include, for example, alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, and polyoxyalkylene alkyl ether sulfates. Aggregation terminating agents may be used alone or in combination of two or more. The aggregation terminator may be added in the form of an aqueous solution.
From the viewpoint of reliably preventing unnecessary aggregation, the amount of the aggregation terminator to be added is preferably based on 100 parts by mass of the total amount of the amorphous resin A, the crystalline polyester resin C, and the amorphous polyester resin B. is 0.1 parts by mass or more, more preferably 1 part by mass or more, and is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, from the viewpoint of reducing residue in the toner.

The volume-median particle diameter (D ₅₀ ) of the aggregated particles 2 is preferably 2 µm or more, more preferably 3 µm or more, still more preferably 4 µm or more, and preferably 10 µm or less, more preferably 8 µm or less, and still more preferably 6 μm or less. The volume-median particle size ( _D50 ) of the aggregated particles is determined by the method described in Examples below.

<Step (3)>
In the step (3), the aggregated particles 2 are fused from the viewpoint of obtaining a wider non-offset temperature range. Note that fusion is usually performed in an aqueous medium.
The fusion temperature is preferably higher than the glass transition temperature of the amorphous resin A, and more preferably 5° C. higher than the glass transition temperature of the amorphous resin A, from the viewpoint of efficiently promoting the fusion of the aggregated particles. More preferably, the temperature is 20°C higher than the glass transition temperature of the amorphous resin A, and preferably 50°C or lower than the glass transition temperature of the amorphous resin A, more preferably the amorphous resin. The temperature is 40° C. higher than the glass transition temperature of A, more preferably 30° C. or lower than the glass transition temperature of amorphous resin A.
It is preferable to monitor the degree of circularity of the fusion-bonded particles, which will be described later, and finish the fusion-bonding when it reaches an appropriate range.

In the step (3), from the viewpoint of neutralizing the aggregated particle dispersion, an acidic substance may be added for fusion.
[Acidic substance]
Examples of acidic substances include inorganic acids and organic acids.
Inorganic acids include, for example, nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid.
Examples of organic acids include carboxylic acid compounds such as monocarboxylic acid, dicarboxylic acid and tricarboxylic acid, sulfonic acid compounds such as methanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid, ascorbic acid, phenol, and cresol. Among these, carboxylic acid compounds are preferred.
Carboxylic acid compounds include, for example, acetic acid, lactic acid, tartaric acid, propionic acid, benzoic acid, oxalic acid, terephthalic acid, fumaric acid, succinic acid, acrylic acid, and adipic acid.
Among these, inorganic acids are preferred, and sulfuric acid is more preferred.

The acidic substance is preferably added to the system as an aqueous solution of the acidic substance.
When the acidic substance is added as an aqueous solution, the concentration of the acidic substance in the aqueous solution of the acidic substance is preferably 0.01 mol/L or more, more preferably 0.03 mol/L or more, and still more preferably 0.05 mol/L or more. Yes, and preferably 1 mol/L or less, more preferably 0.8 mol/L or less, still more preferably 0.5 mol/L or less.

The method of adding the acidic substance may be any of a method of adding all at once, a method of adding the total amount in two or more portions, and a method of continuously adding over a certain period of time. From the viewpoint of suppressing further agglomeration of particles, it is preferable to use either a method of dividing addition or a method of continuously adding over a certain period of time. The temperature at which the acidic substance is added is preferably within the aforementioned fusion temperature range.

The volume median particle size ( _D50 ) of the fused particles obtained by fusion is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably It is 8 μm or less, more preferably 6 μm or less.
The circularity of the fused particles is preferably 0.945 or more, more preferably 0.950 or more, still more preferably 0.955 or more, and preferably 0.990 or less, more preferably 0.980 or less, More preferably, it is 0.975 or less.
The degree of circularity of the fused particles is according to the method described in Examples.
More than seeds may be used.
When the toner particles are surface-treated using an external additive, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 100 parts by mass of the toner particles. It is 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and even more preferably 4 parts by mass or less.

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

EXAMPLES The present invention will be described in more detail with reference to Examples and the like below. In the following examples, etc., the physical properties were measured and evaluated by the following methods. In the following examples, room temperature means a temperature of 20.degree. C. to 25.degree.

[Measuring method]
[Acid value and hydroxyl value of resin]
The acid value and hydroxyl value of the resin were measured according to JIS K0070:1992. However, a mixed solvent of acetone and toluene [acetone:toluene=1:1 (volume ratio)] was used as the measurement solvent.

[Resin softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature increase rate of 6 ° C./min, a load of 1.96 MPa is applied with a plunger, and the diameter It was extruded through a 1 mm, 1 mm long nozzle. The amount of plunger depression of the flow tester was plotted against the temperature, and the softening point was defined as the temperature at which half of the sample flowed out.
(2) Crystallinity index Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 g of the sample was weighed into an aluminum pan, and the cooling rate was 10 ° C./min. was cooled to 0°C. Next, the sample was allowed to stand still for 1 minute, then heated to 180°C at a heating rate of 10°C/min, and the calorific value was measured. Among the observed endothermic peaks, the temperature of the peak with the maximum peak area is defined as the maximum endothermic peak temperature (1), and (softening point (°C)) / (maximum endothermic peak temperature (1) (°C)) A crystallinity index was determined.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 g of the sample was weighed into an aluminum pan and heated to 200 ° C. It was heated and cooled from that temperature to 0°C at a cooling rate of 10°C/min. After that, the temperature was raised at a rate of temperature rise of 10° C./min, and the calorie was measured. Among the observed endothermic peaks, the peak temperature with the maximum peak area was taken as the maximum endothermic peak temperature (2). In the case of a crystalline resin, the peak temperature was taken as the melting point. In the case of an amorphous resin, the glass transition temperature was defined as the temperature at the intersection of the extended line of the baseline below the maximum endothermic peak temperature and the tangent line showing the maximum slope from the rising portion of the peak to the apex of the peak.

[Melting point of release agent]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 g of the sample was weighed into an aluminum pan, heated to 200 ° C., and then cooled from 200 ° C. It was cooled to 0°C at a rate of 10°C/min. Next, the temperature of the sample was increased at a temperature increase rate of 10° C./min, the calorie was measured, and the maximum endothermic peak temperature was defined as the melting point.

[Volume Median Particle Diameter (D50) and CV Value of Resin Particles, Release Agent Particles, Colorant Particles, and Metal Complex Particles]
(1) Measuring device: Laser diffraction particle size measuring machine “LA-920” (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: A sample dispersion was placed in a measurement cell, distilled water was added, and the volume median particle size (D50) and volume average particle size were measured at a temperature at which the absorbance was within the appropriate range. Also, the CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution/volume average particle size) x 100

[Solid Content Concentration of Resin Particle Dispersion, Release Agent Particle Dispersion, Colorant Particle Dispersion, and Metal Complex Particle Dispersion]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), 5 g of the measurement sample is dried at a temperature of 150 ° C., under the conditions of measurement mode 96 (monitoring time 2.5 minutes, fluctuation width 0.05%). , and the water content (% by mass) of the dispersion was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (mass%) = 100 - moisture (mass%)

[Volume-median particle diameter (D ₅₀ ) of aggregated particles]
The volume-median particle size ( _D50 ) of aggregated particles was measured as follows.
・Measuring machine: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・Aperture diameter: 50 μm
・ Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
・ Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured again, and the particle size The volume median particle size ( _D50 ) was determined from the distribution.

[Circularity of Toner Particles (Fusing Particles)]
The circularity of toner particles (fused particles) was measured under the following conditions.
・ Measuring device: Flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation)
Preparation of dispersion liquid: A dispersion liquid of toner particles was diluted with deionized water so as to have a solid content concentration of 0.001 to 0.05% by mass.
・Measurement mode: HPF measurement mode

[Volume Median Particle Diameter ( _D50 ) and CV Value of Toner Particles]
The volume median particle size ( _D50 ) of the toner particles was measured as follows.
The measuring device, aperture diameter, analysis software, and electrolytic solution used were the same as those used in the measurement of the volume-median particle diameter (D ₅₀ ) of the aggregated particles described above.
- Dispersion: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) is dissolved in the electrolytic solution to obtain a dispersion with a concentration of 5% by mass. got
Dispersion conditions: 10 mg of a measurement sample of dried toner particles is added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of an electrolytic solution is added, followed by an ultrasonic disperser. Disperse for 1 minute to prepare a sample dispersion.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. The volume-median particle size ( _D50 ) and volume-average particle size were obtained from the distribution.
Also, the CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution/volume average particle size) x 100

[Evaluation method]
[Low Temperature Fixability of Toner]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 1.49 to 1. A solid image of 0.51 mg/cm ² was output on A4 paper with a length of 50 mm, leaving a margin of 5 mm from the top edge, without being fixed. Next, the same printer with a variable temperature fixing device was prepared, the temperature of the fixing device was set to 100° C., and the toner was fixed at a speed of 1.3 seconds per sheet of A4 paper in the longitudinal direction to obtain printed matter.
By the same method, the temperature of the fixing device was increased by 5° C. to fix the toner, and a printed matter was obtained.
A piece of mending tape "Scotch (registered trademark) Mending Tape 810" (manufactured by Sumitomo 3M Co., Ltd., width 18 mm) cut into a length of 50 mm is lightly pasted from the top margin of the printed image to the solid image. After that, a weight of 500 g (contact area: 1963 mm ² ) was placed and pressed once at a speed of 10 mm/s. After that, the attached tape was peeled off from the lower end side at a peeling angle of 180° and a speed of 10 mm/s to obtain a print after tape peeling. Thirty sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) were placed under the printed matter before and after the tape was applied, and the reflected image density of the fixed image portion of each printed matter was measured before and after the tape was applied. , SpectroEye colorimeter (manufactured by GretagMacbeth, light irradiation conditions; standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard). was calculated.
Fixing rate (%) = (reflected image density after tape removal/reflected image density before tape application) x 100
The lowest temperature at which the fixing rate was 90% or higher was defined as the lowest fixing temperature. The lower the minimum fixing temperature in this test, the better the low-temperature fixability.

[Non-offset temperature range of toner]
The temperature of the fixing device was raised to 200° C. by 5° C. in the same manner as in the low temperature fixability evaluation, and the toner was fixed to obtain a printed matter. The image of the printed matter was visually checked to confirm the temperature at which high-temperature offset occurred, and a temperature 5° C. lower than that temperature was defined as the maximum non-offset temperature. The non-offset temperature width of the toner was calculated according to the following formula.
Non-offset temperature range (°C) = (maximum non-offset temperature) - (minimum fixing temperature)

[Resin production]
Production Example A1 (Production of Amorphous Resin A-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4200 g of propylene oxide (2.2) adduct of bisphenol A, 1355 g of terephthalic acid, di 31 g of (2-ethylhexanoic acid) tin (II) and 3 g of gallic acid (3,4,5-trihydroxybenzoic acid) were added, and the temperature was raised to 235°C under a nitrogen atmosphere while stirring. After holding for 5 hours, the pressure in the flask was lowered and held at 8 kPa for 1 hour. After returning to atmospheric pressure, the system was cooled to 160°C, and a mixture of 1819 g of styrene, 455 g of stearyl methacrylate, 138 g of acrylic acid, and 227 g of dibutyl peroxide was added dropwise over 1 hour while maintaining the temperature at 160°C. Then, after holding at 160° C. for 30 minutes, the temperature was raised to 200° C., the pressure in the flask was further lowered, and the pressure was held at 8 kPa for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 190°C, 223 g of fumaric acid, 230 g of trimellitic anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was raised to 210°C at a rate of 10°C/hr. After that, reaction was carried out at 4 kPa to a desired softening point to obtain an amorphous resin A-1. Various physical properties of the resin were measured and shown in Table 1.

Production Example B1 (Production of Amorphous Resin B-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 5363 g of ethylene oxide (2.2) adduct of bisphenol A, 1780 g of terephthalic acid, di( 2-Ethylhexanoic acid) tin (II) 40 g and gallic acid 4 g were added, and the temperature was raised to 235°C while stirring under a nitrogen atmosphere. It was held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, cool to 180°C, add 287 g of fumaric acid, 221 g of dodecenylsuccinic anhydride, 380 g of trimellitic anhydride, and 2.5 g of 4-tert-butylcatechol, and heat to 220°C by 10°C. /hr, the pressure in the flask was then lowered, and the reaction was carried out at 10 kPa to a desired softening point to obtain an amorphous resin B-1. Various physical properties of the resin were measured and shown in Table 1.

Production Example D1 (Production of Amorphous Resin D-1)
The inside of a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3493 g of a propylene oxide (2.2) adduct of bisphenol A, 662 g of terephthalic acid, and succinic acid were added. Add 589 g of acid, 25 g of di(2-ethylhexanoic acid) tin (II), and 2 g of gallic acid, raise the temperature to 235° C. with stirring under a nitrogen atmosphere, maintain at 235° C. for 5 hours, and place in the flask. was lowered and held at 8 kPa for 1 hour. After returning to atmospheric pressure, the system was cooled to 160°C, and a mixture of 2231 g of styrene, 558 g of stearyl methacrylate, 115 g of acrylic acid, and 334 g of dibutyl peroxide was added dropwise over 1 hour while maintaining the temperature at 160°C. Then, after holding at 160° C. for 30 minutes, the temperature was raised to 200° C., the pressure in the flask was further lowered, and the reaction was carried out to the desired softening point at 8 kPa to obtain amorphous resin D-1. Various physical properties of the resin were measured and shown in Table 1.

Production Example C1 (Production of crystalline polyester resin C-1)
The inside of a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple was replaced with nitrogen, and 3416 g of 1,10-decanediol and 4084 g of sebacic acid were placed therein. The temperature was raised to 135° C. with stirring, held at 135° C. for 3 hours, and then raised from 135° C. to 200° C. over 10 hours. After that, 23 g of di(2-ethylhexanoic acid) tin (II) was added, and the temperature was maintained at 200°C for 1 hour. C-1 was obtained. Various physical properties of the resin were measured and shown in Table 2.

[Production of resin particle dispersion]
Production Example X1 (Production of Resin Particle Dispersion X-1)
210 g of amorphous resin A-1 was added to a container having an internal volume of 3 L equipped with a stirrer "Three One Motor BL300" (manufactured by Shinto Scientific Co., Ltd.), a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube. 90 g of the flexible polyester resin C-1 and 300 g of methyl ethyl ketone were added, and the resins were dissolved at 73° C. for 2 hours. A 5% by mass sodium hydroxide aqueous solution was added to the resulting solution so that the degree of neutralization would be 60 mol % with respect to the acid value of the resin, and the mixture was stirred for 60 minutes.
Then, while maintaining the temperature at 73° C. and stirring at 200 r/min (peripheral speed of 63 m/min), 600 g of deionized water was added over 60 minutes for phase inversion emulsification. While the temperature was maintained at 73° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, after cooling the aqueous dispersion to room temperature while stirring, deionized water was added to adjust the solid content concentration to 30% by mass, and then filtered through a 150-mesh wire mesh to obtain resin particle dispersion X-. got 1. Table 3 shows the volume-median particle size ( _D50 ) and CV value of the obtained resin particles.

Production Examples Y1 and Z1 (Production of Resin Particle Dispersions Y-1 and Z-1)
Resin particle dispersions Y-1 and Z-1 were obtained in the same manner as in Production Example X1, except that the combinations of the amorphous resin and the crystalline polyester resin used were as shown in Table 3. Table 3 shows the volume-median particle size ( _D50 ) and CV value of the obtained resin particles.

[Production of Release Agent Particle Dispersion]
Production Example W1 (Production of Release Agent Particle Dispersion W-1)
120 g of deionized water, 53 g of resin particle dispersion Z-1, and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75 ° C.) were added to a beaker with an internal volume of 1 L, and the temperature was increased to 90 to 95 ° C. The temperature was maintained to melt and stir to obtain a molten mixture. While maintaining the temperature at 90 to 95° C., dispersion treatment was performed for 20 minutes using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then cooled to room temperature. Deionized water was added to the resulting dispersion to adjust the solid content concentration to 20% by mass to obtain release agent particle dispersion W-1. The volume median particle size ( _D50 ) was 0.45 μm and the CV value was 26%.

[Production of colorant particle dispersion]
Production Example P1 (Production of Colorant Particle Dispersion P-1)
In a beaker with an internal volume of 1 L, copper phthalocyanine pigment "ECB-301" (phthalocyanine blue, manufactured by Dainichiseika Kogyo Co., Ltd.) 136.0 g, anionic surfactant "Neoperex (registered trademark) G-15" (Kao Corporation 181.3 g of a 15% by mass sodium dodecylbenzenesulfonate aqueous solution) and 340 g of deionized water were mixed and dispersed for 3 hours at room temperature using a homogenizer, and then dehydrated so that the solid content concentration was 24% by mass. Colorant particle dispersion liquid P-1 was obtained by adding ionized water. The volume median particle size ( _D50 ) of the colorant particles in the dispersion was 0.12 μm.

[Production of metal complex particle dispersion]
Production Example MC1 (Production of Metal Complex Particle Dispersion Liquid MC1)
BONTRON (registered trademark) E-108 (manufactured by Orient Chemical Industry Co., Ltd., aluminum 3,5-di-tert-butylsalicylate), which is a salicylic acid-based metal complex compound, is placed in a beaker having an internal volume of 1 L. complex) 100.0 g, anionic surfactant "Neoperex (registered trademark) G-15" (manufactured by Kao Corporation, 15% by mass sodium dodecylbenzenesulfonate aqueous solution) 133.3 g, and deionized water 268. 5 g of the mixture was mixed and dispersed for 1 hour at room temperature using a homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Primix Co., Ltd.) at a stirring blade rotation speed of 8000 r/min. After that, using a homogenizer “Microfluidizer M-110EH” (manufactured by Microfluidics), a pressure of 150 MPa was applied for 12 passes. After that, the mixture was passed through a 200-mesh filter and deionized water was added so that the solid content concentration became 12% by mass, thereby obtaining a metal complex particle dispersion MC1. Table 4 shows the physical properties of the obtained dispersion.

Production Example MC2 (Production of Metal Complex Particle Dispersion Liquid MC2)
A metal complex particle dispersion MC2 was obtained in the same manner as above, except that the homogenizer was used for 10 passes at a pressure of 140 MPa. Table 4 shows the physical properties of the obtained dispersion.

Production example MC3 (production of metal complex particle dispersion MC3)
A metal complex particle dispersion liquid MC3 was obtained in the same manner as above, except that the dispersing treatment conditions with the homogenizer were 9 passes at a pressure of 120 MPa. Table 4 shows the physical properties of the obtained dispersion.

Production example MC4 (production of metal complex particle dispersion MC4)
A metal complex particle dispersion MC4 was obtained in the same manner as above, except that the homogenizer was subjected to 15 passes at a pressure of 180 MPa. Table 4 shows the physical properties of the obtained dispersion.

Production example MC5 (production of metal complex particle dispersion MC5)
Instead of BONTRON (registered trademark) E-108 as metal complex particles, a complex compound of an alkyl salicylate derivative and iron, BONTRON (registered trademark) X-11 (manufactured by Orient Chemical Industry Co., Ltd., 3,5-di-tert-butylsalicylic acid A metal complex particle dispersion MC5 was obtained in the same manner except that the iron complex) was used. Table 4 shows the physical properties of the obtained dispersion.

Production example MC6 (production of metal complex particle dispersion MC6)
Instead of BONTRON (registered trademark) E-108 as metal complex particles, a complex compound of alkyl salicylate derivative and zinc, BONTRON (registered trademark) E-84 (manufactured by Orient Chemical Industry Co., Ltd., 3,5-di-tert-butylsalicylic acid A metal complex particle dispersion liquid MC6 was obtained in the same manner except that the zinc complex) was used. Table 4 shows the physical properties of the obtained dispersion.

Production Example MC7 (Production of Metal Complex Particle Dispersion Liquid MC7)
A metal complex particle dispersion liquid MC7 was obtained in the same manner as above, except that instead of E-108 as the metal complex particles, a boron-potassium complex compound LR-147 (manufactured by Nihon Carlit Co., Ltd.) was used. Table 4 shows the physical properties of the obtained dispersion.

[Toner production]
Example 1 (Preparation of Toner 1)
300 g of resin particle aqueous dispersion X-1, 50.6 g of release agent particle dispersion W-1, and colorant particles were placed in a four-necked flask with an internal volume of 2 L equipped with a dehydration tube, a stirrer, and a thermocouple. 33.8 g of dispersion liquid P-1, 9.6 g of metal complex particle dispersion liquid MC1, nonionic surfactant "Emulgen (registered trademark) 150" (manufactured by Kao Corporation, polyoxyethylene (average added mole number 50 ) Lauryl ether) 9 g of 10% by mass aqueous solution, 6 g of anionic surfactant "Neopelex G-15" (manufactured by Kao Corporation, sodium dodecylbenzene sulfonate, effective concentration 15% by mass), 150.0 g of deionized water were mixed at room temperature. Next, while stirring the mixture, an aqueous solution of 31.0 g of ammonium sulfate dissolved in 449 g of deionized water was added with 22.4 g of a 4.8% by mass potassium hydroxide aqueous solution to adjust the pH to 8.4. was added dropwise over 15 minutes. Thereafter, the temperature was raised to 62° C. over 2 hours and maintained at 62° C. until the volume median particle diameter (D ₅₀ ) of aggregated particles 1 reached 5.1 μm, to obtain an aggregated particle 1 dispersion liquid.
A mixture of 60.0 g of the resin particle dispersion Y-1 and 18.3 g of deionized water was added over 120 minutes while maintaining the aggregated particle 1 dispersion at 55° C., and the volume of the resin particles aggregated to the aggregated particles was measured. An aggregated particle 2 dispersion having a median particle size (D ₅₀ ) of 5.3 μm was obtained.
17.4 g of an anionic surfactant "Emal (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration: 27% by mass), deionized water An aqueous solution mixed with 590.1 g was added. After that, the temperature was raised to 75° C. over 1 hour. After reaching 75° C., 98.0 g of a 0.1 mol/L sulfuric acid aqueous solution was continuously added over 10 minutes. The circularity is measured while maintaining the temperature at 75° C., and by maintaining the temperature at 75° C. until the circularity reaches the range of 0.965 to 0.975, a dispersion of fused particles in which the aggregated particles 2 are fused is prepared. Obtained.
The obtained dispersion of fused particles is cooled to room temperature, filtered by suction to separate solids, washed with deionized water at 25° C., and vacuum-dried at 35° C. for 48 hours to obtain toner particles. got The volume-median particle diameter ( _D50 ) and CV value of the obtained toner particles were measured. 100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 0.04 μm), and hydrophobic silica “Cabosil (registered trademark) TS720” (Cabot Japan) Co., Ltd., number average particle size; The obtained toner was evaluated, and the results are shown in Table 5.

Examples 2-7, Comparative Examples 1-3
As shown in Table 5, toners were obtained in the same manner as in Example 1 except that the type and amount of the metal complex particle dispersion were changed.

From the results of Examples and Comparative Examples, it can be seen that the present invention can provide a toner having excellent low-temperature fixability and a wide non-offset temperature range.
From Comparative Example 1, the toner containing no salicylic acid-based metal complex particles has no problem in low-temperature fixability, but the non-offset temperature range is narrow. Further, in Comparative Example 2, the toner was produced using the metal complex particle dispersion MC4 in which the content of the salicylic acid-based metal complex particles having a particle size of 80 nm or less in the metal complex particle dispersion was 25% by volume. , a slight increase in minimum fixing temperature and a decrease in non-offset temperature range were observed.
Moreover, in Comparative Example 3, in which a boron/potassium complex was used instead of the salicylic acid-based metal complex, a wide non-offset temperature range could not be obtained.

Claims (5)

mixing a resin particle dispersion containing resin particles X containing an amorphous resin A and a crystalline polyester resin C in the same or different resin particles and a metal complex particle dispersion containing salicylic acid-based metal complex particles, a step of aggregating resin particles X and metal complex particles to obtain aggregated particles 1;
A step of attaching resin particles Y containing an amorphous polyester resin B to the aggregated particles 1 to obtain aggregated particles 2, and a step of fusing the aggregated particles 2 in this order,
The salicylic acid-based metal complex particles in the metal complex particle dispersion have a volume-median particle size of 50 nm or more and 250 nm or less, and the content of the salicylic acid-based metal complex particles having a particle size of 80 nm or less is 20% by volume or less. Yes,
The salicylic acid-based metal complex is a compound represented by the following formula (1),
The amount of the salicylic acid-based metal complex particles added is 1.0 parts by mass or more and 2.5 parts by mass or less with respect to the total amount of 100 parts by mass of all the resin components in the toner .
A method for producing a toner for electrostatic charge image development.

In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, and M represents aluminum. 2. The method for producing a toner for electrostatic charge image development according to claim 1, wherein the metal complex particle dispersion has a pH of 6 or more and 8 or less. 3. The electrostatic image developing device according to claim 1, wherein the salicylic acid-based metal complex particles in the metal complex particle dispersion have a coefficient of variation (CV value (%)) of particle size of 15% or more and 35% or less. Toner manufacturing method. 4. The method for producing a toner for electrostatic charge image development according to claim 1 , wherein said metal complex particle dispersion contains a surfactant. The mass ratio of the crystalline polyester resin C to the amorphous resin A in the resin particles X [crystalline polyester resin C/amorphous resin A] is 5/95 or more and 60/40 or less. 5. A method for producing a toner for developing an electrostatic charge image according to any one of 1 to 4 .