JP2018097153A - Method for manufacturing toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a toner for electrostatic charge image development with which a printed matter with a high image density is obtained.SOLUTION: A method for manufacturing a toner for electrostatic charge image development includes a step of aggregating and fusing particles including resin particles and colorant particles in an aqueous medium; the resin particle contains a composite resin containing a polyester segment, an addition polymerization resin segment that is an addition polymer of a raw material monomer containing a styrene compound, and a unit derived from a bireactive monomer; the colorant particle is obtained by mixing colorant and a compound represented by the formula (1).SELECTED DRAWING: None

Description

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

  In the field of electrophotography, with development of an electrophotographic system, development of a toner for developing an electrostatic image corresponding to high image quality and high speed is demanded. As a method for obtaining a toner having a narrow particle size distribution and a small particle size in response to high image quality, an emulsion aggregation method (coagulation method) in which fine resin particles are aggregated and fused in an aqueous medium to obtain a toner. A toner is manufactured by a gathering method, a cohesive fusion method).

  For example, in Patent Document 1, a toner for developing an electrostatic charge image having a core-shell structure, containing a binder resin containing a composite resin (A) and a crystalline polyester (B) and a wax in a core portion, a polyester resin The binder resin containing (C) is contained in the shell portion, the composite resin (A) is a specific composite resin, the crystalline polyester (B) is a specific crystalline polyester, and the polyester resin (C) However, a toner for developing electrostatic images, which is a specific polyester resin, is described, and the toner for developing electrostatic images is described as having both excellent low-temperature fixability and heat-resistant storage stability and excellent chargeability. ing.

  In Patent Document 2, there is provided a method for producing a toner containing at least a polyester resin and a colorant, wherein (A) a polyester resin and a predetermined ultrahigh molecular weight styrene resin are dissolved in an organic solvent, and a binder resin solution is obtained. (B) a step of dispersing the binder resin solution in an aqueous medium as binder resin solution droplets, and (C) removing the organic solvent from the binder resin solution droplets to obtain a resin. And (D) a step of forming toner particles by aggregating resin particles excluding the organic solvent and colorant particles containing the colorant, to produce a toner. This method describes a toner that has excellent image quality, low-temperature fixability and offset resistance, that is, sufficient fixing temperature range, can be obtained by simple operation, and is advantageous in terms of cost. It has been described as.

Japanese Patent Laid-Open No. 2006-114934 JP 2012-42930 A

In general, in the production of an electrostatic charge image developing toner by an emulsion aggregation method, a colorant is prepared as a dispersion of fine particles, and agglomeration and fusion are carried out in an aqueous medium with resin particles and colorant particles as a binder resin. Let However, there are cases where the image density of the printed image with the obtained toner is not sufficient, and there is a need for a toner production technique that can obtain a higher image density in the emulsion aggregation method.
Therefore, an object of the present invention is to provide a method for producing a toner for developing an electrostatic charge image that can obtain a printed matter having a high image density.

The present inventor has found that the combination of the type of resin used for the binder resin and the type of surfactant used for dispersing the colorant particles has relevance to the toner characteristics such as the image density of the printed matter. It was. More specifically, by using a specific resin and colorant particles obtained by mixing a colorant and a compound represented by the formula (1) (hereinafter also simply referred to as “compound 1”). It has been found that the image density characteristics of the printed matter are improved.
That is, the present invention is a method for producing a toner for developing an electrostatic charge image, comprising a step of aggregating and fusing particles containing resin particles and colorant particles in an aqueous medium,
The resin particles contain a composite resin having an addition polymerization resin segment and a unit derived from both reactive monomers, which are addition polymerization products of raw material monomers containing a polyester segment and a styrene compound,
The present invention relates to a method for producing a toner for developing an electrostatic image, wherein the colorant particles are obtained by mixing a colorant and a compound represented by the following formula (1).

[Wherein, R ¹ is an alkanediyl group having 1 to 12 carbon atoms, m represents an average number of substitutions, the value of m is 1 to 4 and R ² is a hydrogen atom or a methyl group, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of added moles of alkylene oxide, and the value of n is 5 or more and 100 or less. ]

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the electrostatic image developing toner which can obtain the printed matter which has a high image density can be provided.

[Method for producing toner for developing electrostatic image]
The method for producing a toner for developing an electrostatic charge image (hereinafter also simply referred to as “toner”) of the present invention comprises a step of aggregating and fusing particles containing resin particles and colorant particles in an aqueous medium. This is a method for producing a developing toner.
In the production method, the resin particles are a composite resin (hereinafter simply referred to as “composite resin”) having an addition polymerization resin segment which is an addition polymerization product of a raw material monomer containing a polyester segment and a styrene compound, and a unit derived from both reactive monomers. A ”).
In the production method, the colorant particles are obtained by mixing a colorant and a compound represented by the following formula (1) (hereinafter also simply referred to as “compound 1”).

[Wherein, R ¹ is an alkanediyl group having 1 to 12 carbon atoms, m represents an average number of substitutions, the value of m is 1 to 4 and R ² is a hydrogen atom or a methyl group, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of added moles of alkylene oxide, and the value of n is 5 or more and 100 or less. ]
By having such a configuration, it is possible to provide a method for producing a toner for developing an electrostatic charge image, in which a printed matter having a high image density can be obtained.

The reason why the effect of the present invention is obtained is not clear, but is considered as follows.
In the conventional emulsion aggregation method, it has been found that the colorant particles are aggregated when they are aggregated and fused, as one factor that decreases the image density of the obtained toner print. This was thought to be because the colorant was not sufficiently stabilized in the binder resin constituting the toner.
In the present invention, as a resin constituting the binder resin, a composite resin A having an addition polymerization resin segment which is an addition polymerization product of a raw material monomer containing a polyester segment and a styrene compound and a unit derived from both reactive monomers is used. Furthermore, a colorant and a dispersion of colorant particles obtained by mixing the compound 1 having a plurality of aromatic rings in the molecular structure are used in combination. The interaction between the addition polymerization resin segment of the composite resin A and the aromatic ring of the compound 1 makes it easy for the colorant particles to disperse in the resin particles, and prevents aggregation between the colorant particles during aggregation and fusion. It is presumed that the image density of the printed matter has been improved because the dispersibility of the colorant in the obtained toner is improved.

Definitions of various terms and the like in this specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio between the softening point of the resin and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement method described in the examples described later. The crystalline resin is one having a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is one having a crystallinity index of less than 0.6 or greater than 1.4. The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate.
In the specification, the carboxylic acid component of the polyester includes not only the compound but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of 1 to 3 carbon atoms of each carboxylic acid. .

The method for producing an electrostatic image developing toner of the present invention has at least a step of aggregating and fusing particles containing resin particles and colorant particles in an aqueous medium. For example, the method includes the following steps. Good.
Step 1: Step of obtaining composite resin A Step 2: Step of obtaining a dispersion of resin particles (hereinafter also referred to as “resin particles P1”) by dispersing composite resin A in an aqueous medium Step 3: Colorant and compound 1 to obtain a dispersion of colorant particles by mixing Step 1 Step 4: mixing a dispersion containing resin particles P1 and a dispersion containing colorant particles Step 5: resin particles P1 and colorant particles A step of agglomerating the particles containing the particles in an aqueous medium to obtain agglomerated particles (hereinafter also referred to as “aggregated particles 1”) Step 6: a step of fusing the agglomerated particles 1

<Step 1>
In step 1, a composite resin A having an addition polymerization resin segment which is an addition polymerization product of a raw material monomer containing a polyester segment and a styrene compound and a unit derived from both reactive monomers is obtained.

[Composite resin A]
The composite resin A has a polyester segment, an addition polymerization resin segment which is an addition polymerization product of a raw material monomer containing a styrene compound, and a unit derived from both reactive monomers. The composite resin A is preferably an amorphous composite resin.

[Polyester segment]
The polyester segment of the composite resin A is, for example, a polycondensate of an alcohol component (a-al) and a carboxylic acid component (a-ac). Since the composite resin A has a polyester segment, a toner having excellent low-temperature fixability can be obtained.

(Alcohol component (a-al))
Examples of the alcohol component (a-al) include linear or branched aliphatic diols, aromatic diols, alicyclic diols, and trivalent or higher polyhydric alcohols. Among these, an aromatic diol is preferable, and an alkylene oxide adduct of bisphenol A is more preferable from the viewpoint of improving low-temperature fixability and image density of printed matter.
The alkylene oxide adduct of bisphenol A is preferably at least one selected from an ethylene oxide adduct of bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a propylene oxide adduct of bisphenol A, More preferred is a propylene oxide adduct of bisphenol A.

The average addition mole number of alkylene oxide of the alkylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and preferably 16 or less, more preferably It is 12 or less, more preferably 8 or less, and still more preferably 4 or less.
The amount of the alkylene oxide adduct of bisphenol A is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 98 mol% in the alcohol component (a-al). It is above and is 100 mol% or less, More preferably, it is 100 mol%.

The alcohol component (a-al) may contain another alcohol component different from the alkylene oxide adduct of bisphenol A. Examples of other alcohol components include linear or branched aliphatic diols, other aromatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols.
Examples of the linear or branched aliphatic diol 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, , 12-dodecanediol.
Examples of the alicyclic diol include hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), hydrogenated bisphenol A alkylene oxide having 2 to 4 carbon atoms (average added mole number of 2 to 12). The following).
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
These alcohol components can be used alone or in combination of two or more.

(Carboxylic acid component (a-ac))
Examples of the carboxylic acid component (a-ac) include dicarboxylic acids and trivalent or higher polyvalent carboxylic acids.
Examples of the dicarboxylic acid include aromatic dicarboxylic acid, linear or branched aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. Among these, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferable.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and the like. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The amount of the aromatic dicarboxylic acid is preferably 20 mol% or more, more preferably 25 mol% or more, more preferably 30 mol% or more, and preferably 90 mol% in the carboxylic acid component (a-ac). Hereinafter, it is more preferably 70 mol% or less, and still more preferably 50 mol% or less.

The carbon number of 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.
Examples of the linear or branched aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, and sebacic acid. , Succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like. Among these, fumaric acid and sebacic acid are preferable.
Among these, terephthalic acid, sebacic acid, and fumaric acid are preferable, and it is more preferable to use them in combination.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, for example, trimellitic acid.
When a trivalent or higher polyvalent carboxylic acid is included, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more in the carboxylic acid component (a-ac). And, it is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 12 mol% or less.
These carboxylic acid components can be used alone or in combination of two or more.

  The ratio [COOH group / OH group] of the carboxylic acid component (a-ac) to the hydroxyl group of the alcohol component (a-al) is preferably 0.7 or more, more preferably 0.8 or more, and , Preferably 1.3 or less, more preferably 1.2 or less.

[Addition polymerization resin segment]
The addition polymerization resin segment is an addition polymerization product of a raw material monomer containing a styrene compound from the viewpoint of obtaining an excellent printed image density, and preferably a styrene compound and an aliphatic hydrocarbon having 3 to 22 carbon atoms. It is an addition polymerization product of a raw material monomer containing a vinyl monomer having a group.

Examples of the styrene compound include substituted or unsubstituted styrene. Examples of the substituent 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.
Examples of the styrene compound include styrenes such as styrene, methyl styrene, α-methyl styrene, β-methyl styrene, tert-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid or a salt thereof. It is done. Among these, styrene is preferable.
The amount of the styrenic compound is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more in the raw material monomer of the addition polymerization resin segment from the viewpoint of further improving the image density of the printed matter. Yes, and preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

The number of carbon atoms of the hydrocarbon group of the vinyl monomer having an aliphatic hydrocarbon group is preferably 3 or more, more preferably 4 or more, still more preferably 6 or more, and still more preferably, from the viewpoint of further improving the image density of the printed matter. Is 8 or more, more preferably 10 or more, still more preferably 12 or more, still more preferably 14 or more, and is preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.
By containing a vinyl monomer having a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms as a raw material monomer, a microphase separation structure in the composite resin A can be firmly formed. The colorant dispersibility is further improved, and the low-temperature fixability and the image density are improved.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkynyl group, and an alkenyl group, preferably an alkyl group and an alkenyl group, and more preferably an alkyl group. The aliphatic hydrocarbon group may be branched or linear.
The vinyl monomer having an aliphatic hydrocarbon group is preferably an alkyl ester of (meth) acrylic acid. In the case of an alkyl ester of (meth) acrylic acid, the hydrocarbon group is the alcohol side residue of the ester.
Examples of alkyl esters of (meth) acrylic acid include (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, (iso) hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylic acid (iso) octyl (hereinafter also referred to as (meth) acrylic acid 2-ethylhexyl), (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl (hereinafter (meth) acrylic) Acid (iso) lauryl), (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl.
Among these, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl, (meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso ) Behenyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid (iso) dodecyl, (meth) acrylic acid (iso) stearyl are more preferred, (meth) acrylic acid (iso) dodecyl, (meth) Acrylic acid (iso) stearyl is more preferred, and (meth) acrylic acid (iso) stearyl is even more preferred.
Here, “alkyl (meth) acrylate” refers to alkyl acrylate or alkyl methacrylate. In addition, “(iso)” with respect to the alkyl moiety means normal alkyl or isoalkyl.

  The amount of the vinyl monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms is preferably 5% by mass or more, more preferably 5% by mass or more in the raw material monomer of the addition polymerization resin segment from the viewpoint of further improving the image density of the printed matter. Is 10% by mass or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.

  Examples of other raw material monomers include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; ) (Meth) acrylic acid aminoalkyl esters such as dimethylaminoethyl acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinyl pyrrolidone.

  In the raw material monomer in the addition polymerization resin segment, the total amount of the styrene compound and the vinyl monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms is preferably 80 from the viewpoint of further improving the image density of the printed matter. More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, and is 100 mass% or less, More preferably, it is 100 mass%.

[Units derived from both reactive monomers]
The composite resin A has units derived from both reactive monomers from the viewpoint of obtaining an excellent printed image density. When a bi-reactive monomer is used as a raw material monomer of the composite resin A, the bi-reactive monomer reacts with the polyester segment, the addition polymerization resin segment, or each of these raw material monomers to bond the polyester segment and the addition polymerization resin segment. It becomes a point.
The “unit derived from both reactive monomers” means a unit in which the functional group and vinyl moiety of both reactive monomers are reacted.
Examples of the both reactive monomers include vinyl monomers having at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group, and a secondary amino group in the molecule. Among these, from the viewpoint of reactivity, a vinyl monomer having a hydroxyl group or a carboxy group is preferable, and a vinyl monomer having a carboxy group is more preferable.
Examples of the both reactive monomers include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable from the viewpoint of the reactivity of both the polycondensation reaction and the addition polymerization reaction.

  The content of the unit derived from both reactive monomers is preferably 1 mol part or more, more preferably 5 mol, with respect to 100 mol parts of the alcohol component of the polyester segment of the composite resin A from the viewpoint of further improving the image density of the printed matter. The amount is at least mol parts, more preferably at least 8 mol parts, and preferably at most 30 mol parts, more preferably at most 25 mol parts, still more preferably at most 20 mol parts. In addition, when using both reactive monomers and calculating the amount of each segment in the composite resin A, the structural unit derived from the both reactive monomers is calculated as being included in the polyester segment.

The amount of the polyester segment in the composite resin A is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 55% by mass or more, from the viewpoint of further improving the image density of the printed matter. Is 95% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.
The amount of the addition polymerization resin segment in the composite resin A is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, from the viewpoint of further improving the image density of the printed matter. Preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 45 mass% or less.
The total amount of the polyester segment and the addition polymerization resin segment in the composite resin A is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 93% by mass from the viewpoint of further improving the image density of the printed matter. Above, still more preferably 95% by mass or more, and 100% by mass or less, preferably 99% by mass or less.

[Physical properties of composite resin A]
The softening point of the composite resin A is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and preferably 140 ° C. or lower, from the viewpoint of further improving the image density of the printed matter. Preferably it is 130 degrees C or less, More preferably, it is 125 degrees C or less.

  The glass transition temperature of the composite resin A is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, further preferably 40 ° C. or higher, and preferably 70 ° C. or lower, from the viewpoint of further improving the image density of the printed matter. More preferably, it is 60 degrees C or less, More preferably, it is 55 degrees C or less.

  The acid value of the composite 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 from the viewpoint of further improving the image density of the printed matter. 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 composite resin A can be appropriately adjusted according to the production conditions such as the type and amount of the raw material monomer, the reaction temperature, the reaction time, and the cooling rate. A value is calculated | required by the method as described in an Example.
In addition, when using combining 2 or more types of composite resin A, it is preferable that the value of the softening point, glass transition temperature, and acid value which were obtained as those mixtures is in the above-mentioned range, respectively.

[Method of obtaining composite resin A]
The method of obtaining the composite resin A includes, for example, polycondensation with an alcohol component (a-al) and a carboxylic acid component (a-ac), and an addition polymerization reaction with a raw material monomer and an amphoteric monomer of an addition polymerization resin segment. More specifically, the following methods (i) to (iii) may be mentioned.
(I) A method of performing an addition polymerization reaction with a raw material monomer and an amphoteric monomer of an addition polymerization resin segment after a polycondensation reaction with an alcohol component (a-al) and a carboxylic acid component (a-ac). From the viewpoint, it is preferable that both reactive monomers are supplied to the reaction system together with the raw material monomers of the addition polymerization resin segment. From the viewpoint of reactivity, a catalyst such as an esterification catalyst or an esterification cocatalyst may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be further used.
From the viewpoint of further proceeding with the polycondensation reaction and, if necessary, the reaction with both reactive monomers, the carboxylic acid component is partially subjected to the polycondensation reaction, and then the addition polymerization reaction is performed and then the reaction temperature is raised again, The balance is preferably added to the reaction system.

Further, it can be produced by the following method (ii) or (iii).
(Ii) A method of performing a polycondensation reaction with a raw material monomer of a polyester segment after an addition polymerization reaction with a raw material monomer and an amphoteric monomer of an addition polymerization resin segment (iii) A polycondensation reaction and an addition polymerization with an alcohol component and a carboxylic acid component Method of performing addition polymerization reaction in parallel with resin segment raw material monomer and amphoteric monomer The polycondensation reaction and the addition polymerization reaction of the above methods (i) to (iii) are both performed in the same container. Is preferred.
The composite resin A is preferably produced by the above method (i) or (ii) from the viewpoint of a high degree of freedom in the reaction temperature of the polycondensation reaction, and the above (i) is more preferred.

In the polycondensation reaction, the alcohol component (a-al) and the carboxylic acid component (a-ac) are polycondensed. Further, if necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamate is used in an amount of 100 parts by mass of the alcohol component and the carboxylic acid component. 0.01 mass part or more and 5 mass parts or less; esterification cocatalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) is added to 100 mass parts in total of alcohol component and carboxylic acid component 0.001 part by mass or more and 0.5 part by mass or less; if necessary, a radical polymerization inhibitor such as 4-tert-butylcatechol is added in an amount of 0.001 part by mass with respect to 100 parts by mass in total of the alcohol component and the carboxylic acid component. Polycondensation may be carried out using at least 0.5 parts by mass.
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 230 ° C or lower.
The polycondensation may be performed in an inert gas atmosphere.

In the addition polymerization reaction, the raw material monomer and both reactive monomers of the addition polymerization resin segment are subjected to addition polymerization.
The temperature of the addition polymerization reaction is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and preferably 220 ° C. or lower, more preferably 200 ° C. or lower. Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

Examples of the polymerization initiator for the addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile). These known radical polymerization initiators can be used.
The amount of the radical polymerization initiator used is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and preferably 20 parts by mass or less, based on 100 parts by mass of the raw material monomer of the addition polymerization resin segment. Preferably it is 15 mass parts or less.

<Process 2>
Step 2 is a step in which the composite resin A is dispersed in an aqueous medium to obtain a dispersion of resin particles P1.
Here, in addition to the composite resin A, resins that can be used for other toners, for example, other polyester resins, styrene-acrylic copolymers, epoxies, polycarbonates, polyurethanes, and the like may be added.
The amount of the composite resin A is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in the resin component constituting the resin particle P1, from the viewpoint of obtaining an excellent image density of the printed matter. More preferably, it is 98 mass% or more, and preferably 100 mass% or less, and still more preferably 100 mass%.
The amount of the resin component in the resin particle P1 is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and preferably 100%. It is 100 mass% or less, More preferably, it is 100 mass% or less.
As a method of obtaining a dispersion of resin particles P1, for example, a method of adding the composite resin A to an aqueous medium and performing a dispersion treatment with a disperser or the like, or gradually adding an aqueous medium to the organic solvent solution of the composite resin A Although the method of phase inversion emulsification is mentioned, the method by phase inversion emulsification is preferable.

≪Aqueous medium≫
As the aqueous medium, those containing water as a main component are preferable. From the viewpoint of improving the dispersion stability of the dispersion of resin particles and from the viewpoint of environmental properties, the content of water in the aqueous medium is preferably 80% by mass. % Or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and 100% by mass or less, and still more preferably 100% by mass. As water, deionized water or distilled water is preferred.
Examples of components other than water that can be contained in the aqueous medium include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and water such as cyclic ethers such as tetrahydrofuran. Organic solvents to be used.
Among these, from the viewpoint of preventing the organic solvent from being mixed into the toner, an alkyl alcohol having 1 to 5 carbon atoms that does not dissolve the polyester is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

[Phase inversion emulsification]
As the phase inversion emulsification method, for example, after preparing an organic solvent solution of the composite resin A, an aqueous medium is added to the obtained solution to perform phase inversion emulsification, and the aqueous medium is added to the molten composite resin A. And a method of phase inversion emulsification. From the viewpoint of obtaining a homogeneous dispersion of resin particles P1, the former method is preferred.

When the organic solvent is represented by a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc), it is preferably 15.0 MPa ^1/2 or more, more preferably 16.0 MPa ^1/2 or more, More preferably, it is 17.0MPa1 ^{/ 2} or more, Preferably it is 26.0MPa1 ^{/ 2} or less, More preferably, it is 24.0MPa1 ^{/ 2} or less, More preferably, it is 22.0MPa1 ^{/ 2} or less.
Examples of the organic solvent include alcohol solvents such as ethanol (26.0), isopropanol (23.5), isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl isobutyl. Ketone solvents such as ketone (17.2) and diethyl ketone (18.0); ether solvents such as dibutyl ether (16.5), tetrahydrofuran (18.6) and dioxane (20.5); ethyl acetate ( 18.6), and acetate solvents such as isopropyl acetate (17.4). In addition, the numerical value in the parenthesis after each solvent is each SP value (unit: MPa < ^1/2 >). Among these, from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium, at least one selected from ketone solvents and acetate solvents is preferable, and at least one selected from methyl ethyl ketone, ethyl acetate, and isopropyl acetate. Seeds are more preferred, and methyl ethyl ketone is even more preferred.

  In the organic solvent solution, the concentration of the resin is preferably 20% by mass or more, more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less.

  It is preferable to add a neutralizing agent to the organic solvent solution of the resin. Examples of the neutralizing agent include basic substances. Examples of the basic substance include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; nitrogen-containing substances such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, diethanolamine, triethanolamine, and tributylamine. Examples include basic substances. Among these, from the viewpoint of improving the dispersion stability and cohesiveness of the resin particles P1, alkali metal hydroxide is preferable, and sodium hydroxide is more preferable.

The use equivalent amount (mol%) of the neutralizing agent with respect to the acid groups of the resin is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably 120 mol% or less. More preferably, it is 100 mol% or less.
In addition, the use equivalent (mol%) of a neutralizing agent can be calculated | required by a following formula. When the equivalent of the neutralizer is 100 mol% or less, it is synonymous with the degree of neutralization. When the equivalent of the neutralizer exceeds 100 mol% in the following formula, the neutralizer is an acid group of the resin. In this case, the degree of neutralization of the resin is regarded as 100 mol%.
Equivalent (Mole%) of neutralizing agent = [{added mass of neutralizing agent (g) / equivalent of neutralizing agent} / [{weighted average acid value of resin constituting resin particle P1 (mgKOH / g) × Mass of resin composing resin particle P1 (g)} / (56 × 1000)]] × 100

  The amount of the aqueous medium to be added is preferably based on 100 parts by mass of the resin constituting the resin particle P1 from the viewpoint of improving the dispersion stability of the resin particle P1 and obtaining uniform aggregated particles in the subsequent step 5. Is 100 parts by mass or more, more preferably 150 parts by mass or more, still more preferably 200 parts by mass or more, and preferably 900 parts by mass or less, more preferably 600 parts by mass or less.

  Further, from the viewpoint of improving the dispersion stability of the resin particles P1, the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is preferably 20/80 or more, more preferably 50/50 or more, further The ratio is preferably 60/40 or more, and preferably 97/3 or less, more preferably 93/7 or less, and still more preferably 90/10 or less.

  The temperature at which the aqueous medium is added is preferably equal to or higher than the glass transition temperature of the composite resin A constituting the resin particles P1 from the viewpoint of improving the dispersion stability of the resin particles P1. Specifically, the temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 85 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 75. It is below ℃.

  From the viewpoint of obtaining resin particles having a small particle size, the addition rate of the aqueous medium is preferably 0.1 parts by mass / min or more with respect to 100 parts by mass of the resin constituting the resin particles until phase inversion is completed. More preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass. Parts / minute or less. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

  After phase inversion emulsification, it may have a step of removing the organic solvent from the obtained dispersion by distillation or the like, if necessary. In this case, the remaining amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably substantially 0% in the aqueous dispersion.

  The solid content concentration of the dispersion of resin particles P1 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 less, more preferably 40% by mass. It is at most 30% by mass, more preferably at most 30% by mass, even more preferably at most 25% by mass. In addition, solid content is the total amount of non-volatile components, such as resin, a coloring agent, and surfactant.

The volume median particle size D ₅₀ of the resin particles P1 in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, and preferably from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Is 0.80 μm or less, more preferably 0.40 μm or less, still more preferably 0.20 μm or less, and still more preferably 0.15 μm or less.
Here, the volume median particle size D ₅₀ is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size, and is a method described in the examples described later. Desired.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles P1 is preferably 5% or more, more preferably 10% or more, and still more preferably, from the viewpoint of improving the productivity of the dispersion of the resin particles P1. From the viewpoint of obtaining a toner capable of obtaining a high-quality image, it is preferably 50% or less, more preferably 40% or less, and even more preferably 30% or less.
The CV value is a value represented by the following formula. The volume average particle size in the following formula is a particle size obtained by multiplying the particle size measured on a volume basis by the ratio of particles having the particle size value and dividing the value obtained by the number of particles. is there. The CV value is determined by the method described in the examples.
CV value (%) = [standard deviation of particle size distribution (nm) / volume average particle size (nm)] × 100

  The resin particles P1 may contain additives such as a charge control agent, a reinforcing filler such as a fibrous substance, an antioxidant, and an antioxidant, as long as the effects of the present invention are not impaired.

<Step 3>
Step 3 is a step of mixing the colorant and compound 1 to obtain a dispersion of colorant particles.
By using the colorant particles obtained by mixing the colorant and the compound 1, it is considered that the compound 1 adheres to the surface of the colorant particles and the affinity with the resin particles containing the composite resin A is increased.

≪Colorant≫
As the colorant, pigments and dyes are used, and pigments are preferable from the viewpoint of improving the image density of the toner. As the pigment, both inorganic pigments and organic pigments can be used, but organic pigments are preferred.
Examples of inorganic pigments include carbon black and inorganic composite oxides.
As the organic pigment, a yellow pigment, a magenta pigment, a cyan pigment, or the like is used.
Examples of magenta organic pigments include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds, and more. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19. Of these, naphthol compounds are preferred, and C.I. I. Pigment Red 269 is more preferable.

  Examples of cyan organic pigments include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. Among these, a copper phthalocyanine compound is preferable, and C.I. I. Pigment Blue 15: 3 is more preferable.

Examples of the yellow organic pigment include monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, isoindoline compounds, benzimidazolone compounds, anthraquinone compounds, azo metal complexes, and methine compounds, and more specifically. , C.I. I. Pigment yellow 17, 74, 93, 95, 109, 111, 128, 139, 151, 154, 155, 174, 180, 185. Of these, monoazo compounds are preferred, and C.I. I. Pigment Yellow 74 is more preferable.
Examples of the dye include acridine dyes, azo dyes, benzoquinone dyes, azine dyes, anthraquinone dyes, indigo dyes, phthalocyanine dyes, and aniline black dyes.
A coloring agent can be used individually or in combination of 2 or more types.
In the colorant particles, the content of the colorant is preferably 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and preferably 90% by mass or less, more preferably 85%. It is at most 80% by mass, more preferably at most 80% by mass.

<< Compound 1 >>
Compound 1 is a compound represented by the following formula (1) from the viewpoint of functioning as a dispersant for a colorant and obtaining an excellent image density of printed matter.

[Wherein, R ¹ is an alkanediyl group having 1 to 12 carbon atoms, m represents an average number of substitutions, the value of m is 1 to 4 and R ² is a hydrogen atom or a methyl group, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of added moles of alkylene oxide, and the value of n is 5 or more and 100 or less. ]

R ¹ is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 1 to 2 carbon atoms.
Examples of R ¹ include methanediyl group (also referred to as methylene group), ethane-1,1-diyl group, ethane-1,2-diyl group (also referred to as ethylene group), propane-1,1-diyl group, and propane. -1,2-diyl group, propane-1,3-diyl group, butane-1,1-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4- A diyl group and a butane-2,3-diyl group can be mentioned. Among these, a methanediyl group, an ethane-1,1-diyl group, and an ethane-1,2-diyl group are preferable.
The value of m is preferably 2 or more and 3 or less.
R ² is preferably a hydrogen atom.
A ¹ is preferably an ethylene group.
The value of n is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and is preferably 80 or less, more preferably 50 or less, still more preferably 30 or less, and even more preferably 20 or less. is there.

Compound 1 is preferably a compound represented by the following formula (1-1) from the viewpoint of improving the image density of the printed matter.

[Wherein, R ¹ represents a methanediyl group, an ethane-1,1-diyl group, or an ethane-1,2-diyl group, m represents an average number of substitutions, and the value of m is 2 or more and 3 or less. , EO represents an oxyethylene group, n is the average number of moles of ethylene oxide added, and the value of n is 10 or more and 30 or less. ]

Examples of the compound 1 include polyoxyethylene (styrenated phenyl) ether, polyoxyethylene (distyrenated phenyl) ether, polyoxyethylene (distyrenated methylphenyl) ether, polyoxyethylene (tristyrenated phenyl) ether, poly Oxypropylene (styrenated phenyl) ether, polyoxypropylene (distyrenated phenyl) ether, polyoxypropylene (distyrenated methylphenyl) ether, polyoxypropylene (tristyrenated phenyl) ether, polyoxyethylene (benzylphenyl) ether, Polyoxyethylene (dibenzylphenyl) ether, polyoxyethylene (tribenzylphenyl) ether, polyoxypropylene (benzylphenyl) ether, poly Carboxymethyl propylene (dibenzyl) ether, polyoxypropylene (tribenzyl phenyl) ether.
Among these, polyoxyethylene (distyrenated phenyl) ether and polyoxyethylene (tribenzylphenyl) ether are preferable from the viewpoint of improving the image density of the printed matter. The average number of moles added of these polyoxyethylene groups is preferably in the range of n described above.

  As a commercial product of Compound 1, polyoxyethylene (distyrenated phenyl) ether “Emulgen A-60” (average added mole number 13, manufactured by Kao Corporation), polyoxyethylene (distyrenated phenyl) ether “Emulgen A-90” (Average added mole number 18, manufactured by Kao Corporation), polyoxyethylene (tribenzylphenyl) ether “Emulgen B-66” (average added mole number 15, manufactured by Kao Corporation).

  When mixing the colorant and the compound 1, the amount of the compound 1 is preferably 10 parts by mass or more, more preferably 20 parts by mass or more with respect to 100 parts by mass of the colorant, from the viewpoint of further improving the image density of the printed matter. More preferably, it is 25 parts by mass or more, more preferably 30 parts by mass or more, and preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less.

In the step 3, the colorant and the compound 1 are preferably mixed by, for example, mixing the colorant, the compound 1, and the aqueous medium using a disperser to disperse the colorant. By dispersing the colorant with compound 1 to obtain colorant particles, the affinity between the colorant and the composite resin A is increased during aggregation and fusion, and the low-temperature fixability and the image density of the printed matter are further improved. Can be made.
Examples of the disperser include a homomixer, a homogenizer, and an ultrasonic disperser. Examples of suitable commercially available dispersers include homomixer “TKAGI HOMOMIXER 2M-03” (manufactured by Tokushu Kika Kogyo Co., Ltd.), high-pressure homogenizer “Microfluidizer M-110EH” (manufactured by Microfluidics), Ultra A sonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.) can be mentioned.

  The solid content concentration of the colorant particle dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, from the viewpoint of improving the productivity of the toner. Is 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less.

In the dispersion, the volume median particle size D ₅₀ of the colorant particles is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.10 μm or more, and preferably 0.50 μm or less. More preferably, it is 0.30 μm or less, and further preferably 0.25 μm or less.
In the dispersion, the CV value of the colorant particles is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more, and preferably 50% or less, more preferably 40% or less, and further Preferably it is 35% or less.

<Step 4>
Step 4 is a step of mixing the dispersion containing the resin particles P1 and the dispersion containing the colorant particles.
The amount of the colorant particles is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 7 parts by mass or more with respect to 100 parts by mass of the resin particles P1 from the viewpoint of improving the image density of the printed matter. And preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.
In step 4, for example, a dispersion of resin particles other than the resin particles P1 and, if necessary, a dispersion of wax particles are added.

≪Wax particle dispersion≫
(wax)
Examples of the wax include hydrocarbon wax, ester wax, silicone wax, and fatty acid amide wax.
Examples of the hydrocarbon wax include mineral hydrocarbons such as paraffin wax and Fischer-Tropsch wax, and synthetic hydrocarbon waxes such as polyolefin waxes such as polyethylene wax, polypropylene wax, and polybutene wax.
Examples of the ester wax include minerals such as montan wax or petroleum ester wax; plant ester waxes such as carnauba wax, rice wax, and candelilla wax; and animal ester waxes such as beeswax.
Examples of the fatty acid amide wax include oleic acid amide and stearic acid amide.
Among these, from the viewpoint of toner releasability, a hydrocarbon wax or an ester wax is preferable, a hydrocarbon wax is more preferable, and at least one selected from paraffin wax, Fischer-Tropsch wax, and polyolefin wax is more preferable. Even more preferred is a wax.

The melting point of the wax is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher from the viewpoint of toner releasability, and preferably from the viewpoint of improving the low-temperature fixability of the toner. Is 100 ° C. or lower, more preferably 95 ° C. or lower, still more preferably 90 ° C. or lower, and still more preferably 85 ° C. or lower.
The melting point of the wax is determined by the method described in the examples.

  The amount of the wax used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the resin component in the toner from the viewpoint of toner releasability. From the viewpoint of suppressing aggregation and fusion of wax and desorption and exposure of the wax, it is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.

The dispersion of wax particles can be obtained by using a surfactant, but it is possible to obtain a mixture of wax and resin particles _PW described later to flocculate and desorb and expose the wax during fusion. It is preferable from the viewpoint of suppressing.

(Resin particles P _W )
The resin constituting the resin particle _PW is not particularly limited, but is preferably a polyester resin, and from the viewpoint of improving the dispersibility of the wax in an aqueous medium, a composite resin Aw having a polyester segment and an addition polymerization resin segment. It is more preferable to use
The composite resin Aw is preferably an amorphous resin.
As the composite resin Aw, the composite resin exemplified for the composite resin A may be used as it is.
The softening point of the composite resin Aw is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and preferably 140 ° C. or lower, more preferably 120 ° C., from the viewpoint of improving the dispersibility of the wax in the aqueous medium. ° C or lower, more preferably 100 ° C or lower.

The preferred range of other resin properties of the composite resin Aw, the preferred examples of the raw material monomers constituting the resin, and the like are the same as the examples shown for the composite resin A.
The dispersion of the resin particles _PW can be obtained, for example, by the above-described phase inversion emulsification method. Specific conditions and procedures for phase inversion emulsification, that is, the aqueous medium to be used, components other than water that can constitute the aqueous medium, the amount of the aqueous medium, the addition temperature, and the addition rate should also apply the explanations in Step 2 above. Can do.

The solid content concentration of the dispersion of the resin particles _PW is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less.
The volume median particle diameter D ₅₀ of the resin particles P _W is preferably 0.01 μm or more, more preferably 0.03 μm or more, and preferably 0.30 μm from the viewpoint of improving the dispersion stability of the wax particles. Hereinafter, it is more preferably 0.15 μm or less.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles _PW is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more, and preferably 50% or less. More preferably, it is 40% or less, More preferably, it is 30% or less.

(Manufacture of wax particle dispersion)
A dispersion of wax particles is obtained by mixing a wax and a dispersion of resin particles _PW .
And waxes, to prepare a wax particles using resin particles P _W, wax particles are stabilized by resin particles P _W, without using a surfactant wax can be dispersed in an aqueous medium It becomes. It is considered that the wax particle dispersion has a structure in which a large number of resin particles P _W are adsorbed around the wax particles. Thereby, in the subsequent aggregation step, the wax particles are easily taken into the aggregate of the resin particles P1.

The dispersion of wax particles can be obtained, for example, by dispersing a wax, a dispersion of resin particles _PW , and, if necessary, an aqueous medium using a disperser at a temperature equal to or higher than the melting point of the wax. The disperser is preferably a homogenizer, a high-pressure disperser, an ultrasonic disperser, or the like from the viewpoint of the stability of the wax particles, and more preferably an ultrasonic disperser. What is necessary is just to set dispersion | distribution time suitably with the disperser to be used. Examples of the ultrasonic disperser include an ultrasonic homogenizer. Examples of commercially available ultrasonic homogenizers include “US-150T”, “US-300T”, “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.), “SONIFIER (registered trademark) 4020-400”, and “SONIFIER”. (Registered trademark) 4020-800 "(manufactured by Branson).
In addition, before using the disperser, a dispersion of wax and resin particles _PW and, if necessary, an aqueous medium may be preliminarily dispersed in a mixer such as a homomixer or a ball mill in advance. A preferred embodiment of the aqueous medium is the same as that used when obtaining the resin particles P1.

The amount of the resin particles P _W is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more with respect to 100 parts by mass of the wax from the viewpoint of improving the dispersion stability of the wax particles. More preferably, it is 30 parts by mass or more, and preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, and still more preferably 50 parts by mass or less.

  The wax particle dispersion may contain a surfactant, but it is preferable not to contain a surfactant from the viewpoint of suppressing the detachment and exposure of the wax during aggregation and fusion. When the surfactant is contained, the amount of the surfactant with respect to 100 parts by mass of the wax in the wax particles is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and further preferably 0.1 parts by mass or less. And when used for improving the dispersion stability of the wax particles, preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and further preferably 0.05 parts by mass or more. It is.

It is preferable to add the wax and the dispersion liquid of the resin particles _PW to the aqueous medium and disperse while heating at a temperature equal to or higher than the melting point of the wax.
From the viewpoint of improving the productivity of the wax particle dispersion, the heating temperature during dispersion is preferably not less than the melting point of the wax and not less than 80 ° C., more preferably not less than 85 ° C., more preferably not less than 90 ° C., and preferably Is less than the softening point of the resin contained in the resin particles _PW and 100 ° C. or less, more preferably 98 ° C. or less, and still more preferably 95 ° C. or less.

The solid content concentration of the dispersion of wax particles is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass. % Or less, more preferably 25% by mass or less.
The volume median particle size D ₅₀ of the wax particles is preferably 0.05 μm or more, more preferably 0.20 μm or more, still more preferably 0.40 μm or more, and preferably 1.00 μm or less, more preferably 0. .80 μm or less, more preferably 0.60 μm or less.
The coefficient of variation (CV value) (%) of the particle size distribution of the wax particles is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more, and preferably 50% or less, more preferably Is 40% or less, more preferably 30% or less.

The ratio of the volume-median particle size _{D 50} of the volume-median particle size _{D 50} and the resin particles _{P W} of wax particles (volume median particle diameter _{D 50} of the volume-median particle size _{D 50} / resin particles _{P W} of the wax particles) Is preferably 2.0 or more, more preferably 3.0 or more, and preferably 50 or less, more preferably 30 or less, and even more preferably 10 or less, from the viewpoint of improving the dispersion stability of wax particles. is there.

The content of the resin particles P1 in the mixed dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of obtaining aggregation particles having a target particle size by controlling aggregation in the next step 5. More preferably, it is 12% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.
The mass ratio [wax particles / resin particles P1] of the wax particles to the resin particles P1 in the mixed dispersion is preferably 0.05 or more, more preferably 0.10 or more, and preferably 1.0 or less. More preferably, it is 0.5 or less, More preferably, it is 0.2 or less.
The mixing temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, and preferably 40 ° C. or lower, from the viewpoint of controlling aggregation and obtaining aggregated particles having a target particle size. More preferably, it is 30 ° C. or lower.

When preparing the mixed dispersion, the dispersion may be performed in the presence of a surfactant from the viewpoint of improving the dispersion stability of the resin particles P1 and optional components such as wax particles added as necessary.
Examples of the surfactant that can be used include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates, and nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers.
When using a surfactant, 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 P1. It is not more than part by mass, more preferably not more than 5 parts by mass, still more preferably not more than 3 parts by mass.

<Step 5>
Step 5 is a step of obtaining aggregated particles 1 by aggregating particles containing resin particles P1 and colorant particles in an aqueous medium. In this step, a flocculant may be further mixed in an aqueous medium.
Step 5 includes the next step 5A, and may continue to step 5B.
Step 5A: A step of aggregating particles containing resin particles P1 and colorant particles in an aqueous medium, preferably in the presence of wax particles, to obtain agglomerated particles 1c Step 5B: Aggregating particles 1c with a resin (hereinafter referred to as “resin”) Step of obtaining resin particles P2 containing resin particles P2 and adhering the resin particles P2 to obtain aggregated particles 1cs. The aggregated particles 1 include the aggregated particles 1c and the aggregated particles 1cs. Used in the meaning of the concept.

<Step 5A>
Aggregated particles 1c are obtained by mixing and aggregating optional components such as an aggregating agent and a surfactant in a dispersion of particles containing resin particles P1, colorant particles, and wax particles as necessary.

≪Flocculant≫
The flocculant is used from the viewpoint of efficiently performing the aggregation.
Examples of the flocculant include an organic flocculant such as a cationic surfactant of a quaternary salt and polyethyleneimine; an inorganic flocculant such as an inorganic metal salt, an inorganic ammonium salt, and a bivalent or higher metal complex. . From the viewpoint of improving the cohesiveness and obtaining uniform aggregated particles, monovalent to pentavalent inorganic flocculants are preferred, monovalent to divalent inorganic metal salts and inorganic ammonium salts are more preferred, and inorganic ammonium salts are preferred. Further preferred.

Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride, and calcium nitrate, and inorganic metal salt polymers such as polyaluminum chloride and polyaluminum hydroxide.
Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, and ammonium nitrate.
Among these, as the flocculant, ammonium sulfate is more preferable.
From the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle size, the aggregating agent is preferably added dropwise as an aqueous flocculant solution having a mass of 2% by mass to 40% by mass. The aqueous solution of the flocculant preferably has a pH of 7.0 or more and 9.0 or less.

Using a flocculant, for example, 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of resin in the mixed dispersion containing resin particles P1 of 0 to 40 ° C. (preferably 20 to 30 ° C.). The following (preferably 10 parts by mass or more and 40 parts by mass or less) aggregating agent is added, and the particles containing the resin particles P1 are aggregated in an aqueous medium to obtain aggregated particles 1c.
Further, from the viewpoint of promoting aggregation and obtaining aggregated particles having a desired particle size and particle size distribution, it is preferable to increase the temperature of the dispersion after adding the flocculant. The holding temperature is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, further preferably 55 ° C. or higher, and preferably 70 ° C. or lower, more preferably 65 ° C. or lower, still more preferably 60 ° C. or lower. is there.

The volume median particle size D ₅₀ of the aggregated particles 1c 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 even more preferably 6 μm or less. It is. The volume-median particle size of the aggregated particles is determined by the method described in the examples described later.

<Step 5B>
Step 5B is a step of adding aggregated particles 1c to resin particles P2 containing resin As to obtain aggregated particles 1cs obtained by adhering resin particles P2 to aggregated particles 1c.

  By passing through the agglomerated particles 1cs, toner particles having a core-shell structure in which the components of the agglomerated particles 1c are contained in the core part and the resin As is contained in the shell part can be obtained.

≪Resin particles P2≫
The resin particles P2 are preferably obtained as a dispersion liquid of the resin particles P2 by dispersing a resin component containing polyester as the resin As in an aqueous medium.

(Resin As)
The resin As is preferably a polyester that is a polycondensate of an alcohol component (as-al) and a carboxylic acid component (as-ac). The resin As is preferably an amorphous resin.
Examples of the alcohol component (as-al) and the carboxylic acid component (as-ac) are the same as the alcohol component (a-al) and the carboxylic acid component (a-ac) of the composite resin A, but the description thereof is omitted. As resin As, the following aspects are preferable.

The softening point of the resin As is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher, from the viewpoint of improving heat-resistant storage stability, and preferably from the viewpoint of improving low-temperature fixability. Is 160 ° C. or lower, more preferably 140 ° C. or lower, and still more preferably 130 ° C. or lower.
The glass transition temperature of the resin As is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, further preferably 60 ° C. or higher, from the viewpoint of improving the heat resistant storage stability, and from the viewpoint of improving the low-temperature fixability. Preferably it is 90 degrees C or less, More preferably, it is 80 degrees C or less, More preferably, it is 70 degrees C or less.

  From the viewpoint of improving the dispersion stability of the resin particles P2, the acid value of the resin As is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 35 mgKOH. / G or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

The method for obtaining the dispersion is preferably a method in which an aqueous medium is gradually added to the organic solvent solution of the resin and the like is used for phase inversion emulsification, as in the case of the resin particles P1.
As the phase inversion emulsification method, as in the case of the resin particles P1, a method of phase inversion emulsification by adding an aqueous medium to a solution obtained by dissolving the resin and other optional components in an organic solvent is preferable. Preferred embodiments of the aqueous medium and organic solvent that can be used are also the same as the aqueous medium and organic solvent used in the method for producing the resin particles P1. Further, the mass ratio of the aqueous medium to the organic solvent, the temperature at which the aqueous medium is added, and the addition speed of the aqueous medium are the same as in the method for producing the resin particles P1.

Step 5B includes, for example, a dispersion of aggregated particles 1c, a dispersion of resin particles P2 at a temperature of 40 ° C. or higher and 80 ° C. or lower, and 0.03 parts by mass / min or higher with respect to 100 parts by mass of aggregated particles 1c. It is preferable to add the resin particles P2 to the aggregated particles 1c by adding the resin particles P2 at a rate of 1.0 part by mass / min or less to obtain a dispersion of the aggregated particles 1cs.
Before adding the dispersion of resin particles P2, an aqueous medium may be added to the dispersion of aggregated particles 1c to dilute. Further, in order to efficiently attach the resin particles P2 to the aggregated particles 1c, an aggregating agent may be used in Step 5B.

  The addition amount of the resin particles P2 is such that the mass ratio [P2 / P1] of the resin particles P2 and the resin particles P1 is preferably 0.05 or more, more preferably 0.1 or more, and further preferably 0.13 or more. The amount is more preferably 0.15 or more, and preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.2 or less.

The volume median particle size D ₅₀ of the aggregated particles 1s is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Hereinafter, it is more preferably 9 μm or less, and further preferably 8 μm or less.

In step 5, the aggregation may be stopped when the aggregated particles have grown to an appropriate particle size as a toner.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation stopper, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation stopper is preferable.

≪Aggregation stopper≫
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyalkylene alkyl ether sulfate and the like.
An aggregation terminator can be used individually or in combination of 2 or more types.

  The addition amount of the aggregation terminator is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the total amount of the resin in the toner, from the viewpoint of surely preventing unnecessary aggregation. More preferably, it is 2 parts by mass or more, and from the viewpoint of reducing residual toner, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less. The aggregation terminator may be added as an aqueous solution.

The temperature at which the aggregation terminator is added is preferably the same as the temperature at which the dispersion liquid of the aggregated particles is retained from the viewpoint of improving the productivity of the toner. The said temperature becomes like this. Preferably it is 40 degreeC or more, More preferably, it is 45 degreeC or more, More preferably, it is 50 degreeC or more, Preferably it is 80 degreeC or less, More preferably, it is 70 degreeC or less, More preferably, it is 65 degreeC or less.
Further, from the viewpoint of stabilizing the aggregated particles and preventing the aggregated particles from being dispersed before fusion, it is preferable to add an acid together with the stop of aggregation to make the dispersion of the aggregated particles neutral to acidic. .
The acid to be added is not limited, and examples thereof include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and acetic acid. From the viewpoint of rapid pH change with respect to addition, hydrochloric acid, sulfuric acid, nitric acid, and acetic acid are preferred. And at least one selected from hydrochloric acid, sulfuric acid, and nitric acid, and more preferably sulfuric acid.
The acid is preferably added in the form of an aqueous solution. Further, it may be added together with an aggregation terminator.

<Step 6>
Step 6 is a step of fusing the aggregated particles 1.
Here, the aggregated particles 1 are aggregated particles 1c when the step 5B is not performed, and are aggregated particles 1cs when the step 5B is performed.
In step 6, the particles in the aggregated particles 1 that are mainly physically attached to each other are fused and united to form fused particles.
When the aggregated particles 1cs are fused, toner particles having a core-shell structure can be obtained.

The fusion temperature is preferably at least 5 ° C. higher than the glass transition temperature of the composite resin A from the viewpoint of promoting fusion of the aggregated particles 1. More preferably, the fusing temperature is at least 10 ° C. higher than the glass transition temperature of the composite resin A, more preferably at least 20 ° C. higher than the glass transition temperature of the composite resin A, and more preferably the composite resin A. The temperature is 40 ° C. or higher than the glass transition temperature of A.
The holding time is not particularly limited, and the degree of circularity of the fused particles may be monitored, and the fusion may be terminated when it reaches an appropriate range.

The volume median particle size D ₅₀ of the fused particles 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 even more preferably 6 μm or less. It is.
The circularity of the fused particles is preferably 0.955 or more, more preferably 0.960 or more, still more preferably 0.965 or more, and preferably 0.990 or less, more preferably 0.985 or less, More preferably, it is 0.980 or less.

<Post-processing process>
A post-treatment step may be performed after step 6, and it is preferable to obtain toner particles by isolating the fused particles from the dispersion obtained in step 6.
Since the fused particles in the dispersion obtained in step 6 are present in the aqueous medium, it is preferable to first perform solid-liquid separation. For solid-liquid separation, a suction filtration method or the like is preferably used.
It is preferable to perform washing after the solid-liquid separation. At this time, since it is preferable to remove the added surfactant, it is preferable to wash with an aqueous medium below the cloud point of the surfactant. The washing is preferably performed a plurality of times.

Next, it is preferable to perform drying. The drying temperature is preferably such that the temperature of the fused particles themselves is lower than the minimum glass transition temperature of the resin constituting the resin particles. Examples of the drying method include a vacuum low temperature drying method, a vibration type fluidized drying method, a spray drying method, a freeze drying method, and a flash jet method. The water content after drying is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of improving the chargeability of the toner.
By drying the fused particles, toner particles can be obtained.

As a post-processing step, a step of mixing toner particles and an external additive may be included.
Examples of the external additive include inorganic fine particles such as hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable.
When the external additive is used, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the toner particles. The amount is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and still more preferably 4 parts by mass or less.

[Toner for electrostatic image development]
<Toner particles>
The toner particles obtained by the above-described method can be used directly as a toner for developing an electrostatic image, but it is preferable to use the toner particles whose surface has been treated as described above as a toner for developing an electrostatic image.

The volume median particle size D ₅₀ of the toner particles 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 from the viewpoint of obtaining a high-quality image. It is 8 μm or less, more preferably 6 μm or less.
From the viewpoint of obtaining a high-quality image, the CV value of the toner particles is preferably 12% or more, more preferably 14% or more, still more preferably 16% or more, and preferably 30% or less, more preferably 26 % Or less.
The circularity of the toner particles is preferably 0.955 or more, more preferably 0.960 or more, and still more preferably 0.965 or more from the viewpoint of obtaining a high-quality image, and from the viewpoint of toner cleaning properties. , Preferably 0.990 or less, more preferably 0.985 or less, and still more preferably 0.980 or less.

  The toner is used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method or the like. The toner can be used as a one-component developer or as a two-component developer mixed with a carrier.

Each property value was measured and evaluated by the following method.
In addition, in the notation of “polyoxyalkylene (X)”, the numerical value X in parentheses means the average number of added moles of alkylene oxide.

[Acid value]
The acid value of the resin was measured according to the neutralization titration method described in JIS K 0070-1992. However, the measurement solvent was chloroform.

[Softening point, crystallinity index, melting point and glass transition temperature of resin]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. Extruded from a nozzle of 1 mm length 1 mm. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Crystallinity Index Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample is weighed into an aluminum pan, and the temperature lowering rate from room temperature (25 ° C.) is 10 ° C. / Cooled to 0 ° C. in min. Next, the sample was allowed to stand still for 1 minute, and then heated to 180 ° C. at a heating rate of 10 ° C./min, and the amount of heat was measured. Of the observed endothermic peaks, the temperature of the peak with the largest peak area is defined as the maximum endothermic peak temperature (1), and (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)), The crystallinity index was determined.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature Then, it was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the sample was heated at a temperature rising rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic temperature (2). In the case of a crystalline resin, the peak temperature was taken as the melting point.
In the case of an amorphous resin, when the peak is observed, the temperature of the peak is measured, and when the step is observed without the peak being observed, the tangent indicating the maximum slope of the curve of the step and the step The temperature at the intersection with the extension of the base line on the low temperature side was defined as the glass transition temperature.

[Melting point of wax]
Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and then cooled down from 200 ° C. to 10 ° C./min. At 0 ° C. Next, the sample was heated at a temperature rising rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[Volume Median Particle Size D ₅₀ and CV Value of Resin Particles, Colorant Particles, and Wax Particles]
(1) Measuring apparatus: Laser diffraction type particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
(2) Measurement conditions: Distilled water was added to the measuring cell, the absorbance was measured volume-median particle size D ₅₀ and the volume average particle size in a concentration comprised within a proper range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Solid content concentration of resin particle dispersion, colorant particle dispersion, and wax particle dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Scientific Laboratory Co., Ltd.), a measurement sample 5 g was dried at a temperature of 150 ° C., a measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of moisture content 0.05% ), Moisture (mass%) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-water content (% by mass)

[Volume Median Particle Size D _{50 of} Aggregated Particles]
The volume median particle diameter D ₅₀ of aggregated particles was measured as follows.
Measuring instrument: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
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: After adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte, 30,000 particles are measured again, and the particle size The volume median particle size D ₅₀ was determined from the distribution.

[Volume Median Particle Size D ₅₀ and CV Value of Toner Particles]
Volume-median particle size D ₅₀ of the toner particles was measured as follows.
Measuring device, aperture diameter, analysis software, the electrolytic solution used was the same as that used in the measurement of the volume-median particle size 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) was dissolved in the electrolyte solution, and a dispersion solution having a concentration of 5% by mass was dissolved. Obtained.
-Dispersion condition: 10 mg of a measurement sample of toner particles after drying is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 mL of electrolyte is added, and further, with an ultrasonic disperser. A sample dispersion was prepared by dispersing for 1 minute.
Measurement conditions: After adding the sample dispersion to 100 mL of the electrolyte 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 D ₅₀ and the volume average particle size were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Image density of printed matter]
First, the following fixing test was performed to set a minimum fixing temperature.
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 1.48 to 1. A solid image of .52 mg / cm ² was output without being fixed at a length of 50 mm, leaving a margin of 5 mm from the top edge of A4 paper.
Next, the same printer having a temperature-variable fixing device was prepared. The temperature of the fixing device was set to 110 ° C., and the toner was fixed at a speed of 1.2 seconds per sheet in the A4 longitudinal direction to obtain a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C. to fix the toner, and a printed matter was obtained.
From the margin at the top edge of the printed image to the solid image, lightly paste the mending tape “Scotch (registered trademark) mending tape 810” (manufactured by Sumitomo 3M Limited, width 18 mm) to a length of 50 mm. After that, a 500 g weight was placed and pressed once back and forth at a speed of 10 mm / s. Thereafter, the affixed 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 printed matter after peeling off the tape. 30 sheets of high quality paper “Excellent White Paper A4 Size” (made by Oki Data Co., Ltd.) is laid under the printed material before and after the tape is applied, and the reflected image density of the fixed image portion before and after the tape is applied to each printed material. , Using a colorimeter “SpectroEye” (manufactured by GretagMacbeth, light conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and fixing rate from each reflected image density according to the following formula Was calculated.
Fixing rate (%) = (Reflected image density after peeling tape / Reflected image density before applying tape) × 100
The lowest temperature at which the fixing rate was 90% or more was defined as the lowest fixing temperature.
Next, using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Co., Ltd.) on a high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhering to the paper is 0.00. A solid image of 35 mg / cm ² was output.
The temperature of the fixing device was set to the minimum fixing temperature + 10 ° C. obtained in the fixing test, and the toner was fixed at a speed of 1.2 seconds per sheet in the A4 longitudinal direction to obtain a printed matter.
30 sheets of high quality paper “Excellent White Paper A4 Size” (Oki Data Co., Ltd.) was laid under the printed material, and the reflected image density of the solid image portion of the printed material was measured using a colorimeter “SpectroEye” (manufactured by GretagMacbeth, Hikari Shooting conditions: standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and measured values of 10 arbitrary points on the image were averaged to obtain an image density. The larger the value, the better the image density.

[Production of resin (including step 1)]
Production Example A1
(Production of composite resin A-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3302 g of a polyoxypropylene (2.2) adduct of bisphenol A, 595 g of terephthalic acid, 25 g of di (2-ethylhexanoic acid) tin (II) and 2.5 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. while stirring in a nitrogen atmosphere. After holding for a period of time, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Thereafter, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and maintained at 160 ° C., and a mixture of styrene 2198 g, stearyl methacrylate 550 g, acrylic acid 109 g, and dibutyl peroxide 330 g was added dropwise over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., and the pressure in the flask was further lowered and maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, it cooled to 190 degreeC, 241 g of fumaric acid, 572 g of sebacic acid, 181 g of trimellitic anhydride, and 2.5 g of 4-tert- butyl catechol were added, and 10 degreeC / hr to 210 degreeC. And then reacted at 4 kPa to the desired softening point to obtain composite resin A-1. The physical properties are shown in Table 1.

Production Examples A2 to A5
(Production of composite resins A-2 to A-5)
Composite resins A-2 to A-5 were obtained in the same manner as in Production Example A1, except that the raw material composition was changed as shown in Table 1. The physical properties are shown in Table 1.

Production Example A6
(Production of resin A-6)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 5405 g of a polyoxypropylene (2.2) adduct of bisphenol A, 769 g of terephthalic acid, 30 g of di (2-ethylhexanoic acid) tin (II) and 3.0 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. while stirring in a nitrogen atmosphere. After holding for a period of time, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, it cooled to 190 degreeC, fumaric acid 197g, sebacic acid 1404g, trimellitic anhydride 296g, and 4-tert- butyl catechol 3.8g were added, and 10 degreeC / hr to 220 degreeC. After that, the pressure in the flask was lowered and the reaction was carried out at 10 kPa to the desired softening point to obtain Resin A-6. The physical properties are shown in Table 1.

Production Example A7
(Production of resin A-7)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, 3316 g of a polyoxypropylene (2.2) adduct of bisphenol A, 598 g of terephthalic acid, 25 g of di (2-ethylhexanoic acid) tin (II) and 2.5 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. while stirring in a nitrogen atmosphere. After holding for a period of time, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture of styrene 2197g, stearyl methacrylate 549g, and dibutyl peroxide 330g was dripped over 1 hour in the state which cooled to 160 degreeC and was hold | maintained at 160 degreeC. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., and the pressure in the flask was further lowered and maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, it cooled to 190 degreeC, fumaric acid 330g, sebacic acid 574g, trimellitic anhydride 182g, and 4-tert- butyl catechol 3.5g were added, and 10 degreeC / hr to 210 degreeC. Then, the reaction was carried out at 4 kPa to the desired softening point to obtain Resin A-7. The physical properties are shown in Table 1. Resin A-7 exhibited two glass transition temperatures.

Production Example A8
(Production of composite resin A-8)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 4313 g of a polyoxypropylene (2.2) adduct of bisphenol A, 818 g of terephthalic acid, 727 g of succinic acid, 30 g of di (2-ethylhexanoic acid) tin (II), and 3.0 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. with stirring in a nitrogen atmosphere. After holding at 235 ° C. for 5 hours, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture of styrene 2756g, stearyl methacrylate 689g, acrylic acid 142g, and dibutyl peroxide 413g was dripped over 1 hour in the state which cooled to 160 degreeC and was hold | maintained at 160 degreeC. Then, after maintaining 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 at 8 kPa to the desired softening point to obtain composite resin A-8. The physical properties are shown in Table 1.

[Production of resin particle dispersion (step 2)]
Production Example X1
(Production of resin particle dispersion X-1)
300 g of composite resin A-1, 360 g of methyl ethyl ketone, and 49 g of deionized water were placed in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube. The resin was dissolved over time. A 5% by mass aqueous sodium hydroxide solution was added to the resulting solution so that the degree of neutralization was 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Next, while maintaining at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r / min (circumferential speed 63 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (circumferential speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid X-1 was obtained. Table 2 shows the volume-median particle size D ₅₀ and CV value of the obtained resin particles.

Production Examples X2 to X7
(Production of resin particle dispersions X-2 to X-7)
Resin particle dispersions X-2 to X-7 were obtained in the same manner as in Production Example X1, except that the resin used was changed as shown in Table 2. Table 2 shows the volume-median particle size D ₅₀ and CV value of the obtained resin particles.

Production Example Y1
(Production of resin particle dispersion Y-1)
200 g of composite resin A-8 and 200 g of methyl ethyl ketone are placed in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, and the resin is dissolved at 73 ° C. over 2 hours. I let you. 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so that the neutralization degree might be 60 mol% with respect to the acid value of composite resin A-8, and it stirred for 30 minutes.
Next, while maintaining at 73 ° C., 700 g of deionized water was added over 50 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid Y-1 was obtained. Table 2 shows the volume-median particle size D ₅₀ and CV value of the obtained resin particles.

[Production of wax particle dispersion]
Production Example D1 (Production of Wax Particle Dispersion D-1)
120 g of deionized water, 86 g of resin particle dispersion Y-1 and 40 g of paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C.) are added to a beaker having an internal volume of 1 L, and 90 to 95 ° C. The mixture was melted while maintaining the temperature and stirred to obtain a molten mixture.
The obtained molten mixture was further dispersed for 20 minutes using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusyo Co., Ltd.) while maintaining the temperature at 90 to 95 ° C. until room temperature (20 ° C.). Cooled down. Deionized water was added to adjust the solid content concentration to 20% by mass to obtain a wax particle dispersion D-1. The volume median particle size D ₅₀ of the wax particles in the dispersion was 0.47 μm, and the CV value was 27%.

[Production of Colorant Particle Dispersion (Step 3)]
Production Example Z1
(Production of Colorant Particle Dispersion Z-1)
In a beaker with an internal volume of 1 L, magenta pigment “Permanent Carmine 3810” (Sanyo Dye, CI Pigment Red 269) 100 g, polyoxyethylene (13) distyrenated phenyl ether “Emulgen A-60” (Kao Stock) 35 g of nonionic surfactant (manufactured by company) and 300 g of deionized water are mixed, and a stirring blade is used at room temperature using a homomixer “TKAGI HOMOMIXER 2M-03” (manufactured by Tokushu Kika Kogyo Co., Ltd.). After being dispersed for 1 hour at a rotational speed of 8000 rpm, after being subjected to 15 PASS treatment at a pressure of 150 MPa using “Microfluidizer M-110EH” (manufactured by Microfluidics), it was passed through a 200-mesh filter to a solid content concentration of 24% by mass. To add deionized water to Ri to obtain a colorant particle dispersion Z-1. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles shown in Table 3.

Production Example Z2
(Production of Colorant Particle Dispersion Z-2)
A colorant is produced in the same manner as in Production Example Z1, except that the surfactant to be added is changed to polyoxyethylene (18) distyrenated phenyl ether “Emulgen A-90” (manufactured by Kao Corporation, nonionic surfactant). A particle dispersion Z-2 was obtained. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles shown in Table 3.

Production Example Z3
(Production of Colorant Particle Dispersion Z-3)
A colorant was prepared in the same manner as in Production Example Z1, except that the surfactant to be added was changed to polyoxyethylene (15) tribenzylphenyl ether “Emulgen B-66” (manufactured by Kao Corporation, nonionic surfactant). A particle dispersion Z-3 was obtained. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles shown in Table 3.

Production Example Z4
(Production of Colorant Particle Dispersion Z-4)
Colorant particle dispersion Z-4 was obtained in the same manner as in Production Example Z1, except that the amount of surfactant added was changed from 35 g to 20 g. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles shown in Table 3.

Production Example Z5
(Production of Colorant Particle Dispersion Z-5)
Colorant particle dispersion Z-5 was obtained in the same manner as in Production Example Z1, except that the colorant was changed to 100 g of cyan pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd., copper phthalocyanine pigment). Volume-median particle size D ₅₀ and CV value of the obtained colorant particles shown in Table 3.

Production Example Z6
(Production of Colorant Particle Dispersion Z-6)
A colorant particle dispersion liquid Z-6 was obtained in the same manner as in Production Example Z1, except that the colorant was changed to 100 g of yellow pigment “HANSA YELLOW 5GX01” (CI Pigment Yellow 74, manufactured by Clariant Chemicals Co., Ltd.). It was. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles shown in Table 3.

Production Example Z7
(Production of Colorant Particle Dispersion Z-7)
In a beaker with an internal volume of 1 L, magenta pigment “Permanent Carmine 3810” (Sanyo Dye, CI Pigment Red 269) 100 g, 15% by mass sodium dodecylbenzenesulfonate aqueous solution “Neopelex G-15” (Kao Corporation) 233 g of an anionic surfactant (manufactured by company) and 102 g of deionized water were mixed, and the stirring blade was stirred at room temperature using a homomixer “TKAGI HOMOMIXER 2M-03” (manufactured by Tokushu Kika Kogyo Co., Ltd.). After being dispersed for 1 hour at a rotational speed of 8000 rpm, after being subjected to 15 PASS treatment at a pressure of 150 MPa using “Microfluidizer M-110EH” (manufactured by Microfluidics), it was passed through a 200-mesh filter to a solid content concentration of 24% by mass. Add deionized water so that To obtain a colorant particle dispersion Z-7 by. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles shown in Table 3.

Production Example Z8
(Production of Colorant Particle Dispersion Z-8)
In a beaker with an internal volume of 1 L, magenta pigment “Permanent Carmine 3810” (Sanyo Dye, CI Pigment Red 269) 100 g, polyoxyethylene (13) oleyl ether “Emulgen 420” (Kao Corporation, Nonion) Active surfactant) 35 g of deionized water dissolved in 300 g is added and mixed, and then at room temperature using a homomixer “TK AG HOMOMIXER 2M-03” (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, the mixture was dispersed for 1 hour at a rotation speed of the stirring blade at 8000 rpm, treated with 15 PASS at a pressure of 150 MPa using “Microfluidizer M-110EH” (manufactured by Microfluidics), passed through a 200 mesh filter, and the solid content concentration was 24 Add deionized water to a mass%. To obtain a colorant particle dispersion Z-8 by Rukoto. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles shown in Table 3.

[Production of toner]
Example 1
(Preparation of Toner 1)
Into a 3 L four-necked flask equipped with a dehydrating tube, a stirrer and a thermocouple, 300 g of resin particle dispersion X-1, 34 g of wax particle dispersion D-1 and colorant particle dispersion Z-1 30 g and 6 g of a 10% by mass aqueous solution of polyoxyethylene (50) lauryl ether “Emulgen 150” (manufactured by Kao Corporation, nonionic surfactant) were mixed at a temperature of 25 ° C. (step 4). Next, while stirring the mixture, a solution adjusted to pH 8.6 by adding 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution in which 19 g of ammonium sulfate was dissolved in 179 g of deionized water was added at 25 ° C. for 5 minutes. Then, the temperature was raised to 60 ° C. over 2 hours, and kept at 60 ° C. until the volume median particle size D _{50 of} the aggregated particles became 5.2 μm, whereby a dispersion of aggregated particles was obtained (above) Step 5).
10 g of polyoxyethylene lauryl ether sulfate “Emar E-27C” (manufactured by Kao Corporation, anionic surfactant, effective concentration: 27% by mass), 980 g of deionized water, and 0 An aqueous solution mixed with 40 g of a 1 mol / L sulfuric acid aqueous solution was added. Thereafter, the temperature was raised to 75 ° C. over 1 hour, and held at 75 ° C. until the circularity became 0.970, thereby obtaining a dispersion of fused particles in which the aggregated particles were fused (the above process). 6).
The obtained fused particle dispersion was cooled to 30 ° C., and the dispersion was subjected to suction filtration to separate the solid content, then washed with deionized water at 25 ° C., and suction filtered at 25 ° C. for 2 hours. Thereafter, using a vacuum constant temperature dryer “DRV622DA” (manufactured by ADVANTEC), vacuum drying was performed at 33 ° C. for 24 hours to obtain toner particles. Table 4 shows the physical properties of the obtained toner particles.
100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size: 0.04 μm), and hydrophobic silica “Cabosil® TS720” (Cabot Japan Co., Ltd.) 1.0 part by mass (manufactured by company, number average particle diameter; 0.012 μm) was put in a Henschel mixer and stirred, and passed through a 150-mesh sieve to obtain toner 1. The evaluation results of the obtained toner 1 are shown in Table 4.

Examples 2, 3, 5-10, Comparative Examples 1-4
(Production of toners 2, 3, 5 to 14)
A toner was prepared in the same manner as in Example 1 except that the type of resin particle dispersion used and the type of colorant particle dispersion were changed as shown in Table 4. Table 4 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 4
(Preparation of Toner 4)
A toner was prepared in the same manner as in Example 1 except that the colorant particle dispersion used was changed to Z-4 and the amount was changed to 27 g. Table 4 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

  From the results of Examples and Comparative Examples, when Compound 1 is used as the dispersant for the colorant particle dispersion, both the addition polymerization resin segment, which is an addition polymer of a raw material monomer containing a polyester segment and a styrene compound, are reacted. It can be seen that a toner exhibiting a high image density of a printed matter can be obtained by using together with resin particles containing a composite resin having a unit derived from a functional monomer.

Claims (6)

A method for producing a toner for developing an electrostatic charge image, comprising a step of aggregating and fusing particles containing resin particles and colorant particles in an aqueous medium,
The resin particles contain a composite resin having an addition polymerization resin segment and a unit derived from both reactive monomers, which are addition polymerization products of raw material monomers containing a polyester segment and a styrene compound,
A method for producing a toner for developing an electrostatic charge image, wherein the colorant particles are obtained by mixing a colorant and a compound represented by the following formula (1).

[Wherein, R ¹ is an alkanediyl group having 1 to 12 carbon atoms, m represents an average number of substitutions, the value of m is 1 to 4 and R ² is a hydrogen atom or a methyl group, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of added moles of alkylene oxide, and the value of n is 5 or more and 100 or less. ]   The method for producing a toner for developing an electrostatic charge image according to claim 1, further comprising a step of mixing a dispersion containing resin particles and a dispersion containing colorant particles before the step of aggregating and fusing. .   The method for producing a toner for developing an electrostatic charge image according to claim 1 or 2, wherein in the addition polymerization resin segment, the amount of the styrene compound is 50% by mass or more in the raw material monomer.   4. The electrostatic charge image developing toner according to claim 1, wherein in the addition polymerization resin segment, the raw material monomer further contains a vinyl monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms. Production method.   The method for producing a toner for developing an electrostatic charge image according to claim 4, wherein the vinyl monomer has an aliphatic hydrocarbon group having 8 to 22 carbon atoms.   When mixing the colorant and the compound represented by the formula (1), the amount of the compound represented by the formula (1) is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the colorant. A method for producing a toner for developing an electrostatic charge image according to claim 1.