JP6784371B2 - Manufacturing method of toner for static charge image development - Google Patents

Description

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

In the field of electrophotographic, with the development of electrophotographic systems, there is a demand for the development of toner for static charge image development corresponding to high image quality and high speed. As a method for obtaining toner having a narrow particle size distribution and a small particle size in response to higher image quality, an emulsion aggregation method (coagulation) in which fine resin particles and the like are aggregated and fused in an aqueous medium to obtain toner. Toners are manufactured by the aggregation method (aggregation fusion method).

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

Patent Document 2 is a method for producing a toner containing at least a polyester resin and a colorant. In (A) an organic solvent, a polyester resin and a predetermined ultrahigh molecular weight styrene resin are dissolved to form a binder resin solution. (B) The step of dispersing the binder resin solution as a binder resin solution droplet in an aqueous medium, and (C) the step of removing the organic solvent from the binder resin solution droplets to make a resin. Manufacture of a toner comprising a step of producing a particle dispersion liquid and (D) a step of forming toner particles by aggregating the resin particles from which the organic solvent has been removed and the colorant particles containing the colorant. A method is described, and the manufacturing method provides a toner having excellent image quality, low temperature fixability and offset resistance, that is, a sufficient fixable temperature range, a simple operation, and an advantage in terms of cost. It is stated that it will be done.

JP-A-2016-114934 Japanese Unexamined Patent Publication No. 2012-42930

Generally, in the production of a toner for developing an electrostatic charge image by an emulsion aggregation method, a colorant is prepared as a dispersion of fine particles, and aggregated and fused with resin particles and colorant particles to be a binder resin in an aqueous medium. Let me. However, the image density of the printed image by the obtained toner may not be sufficient, and in the emulsion aggregation method, a toner manufacturing technique capable of obtaining a higher image density is required.
Therefore, an object of the present invention is to provide a method for producing a toner for developing an electrostatic charge image, which 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 is related to the characteristics of the toner such as the image density of 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 printed matter are improved.
That is, the present invention is a method for producing a toner for static charge image development, which comprises 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 which is an addition polymerization of a raw material monomer containing a polyester segment and a styrene compound and a unit derived from a bireactive monomer.
The present invention relates to 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).

[In the formula, R ¹ is an alcoholic group having 1 or more and 12 or less carbon atoms, m indicates the average number of substitutions, m has a value of 1 or more and 4 or less, and R ² is a hydrogen atom or 1 or more and 12 carbon atoms. The following alkyl groups, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of moles of alkylene oxide added, and the value of n is 5 or more and 100 or less. , M is ammonium, tetraalkylammonium, or alkali metal. ]

According to the present invention, it is possible to provide a method for producing a toner for developing an electrostatic charge image, which can obtain a printed matter having a high image density.

[Manufacturing method of toner for static charge image development]
The method for producing a toner for developing an electrostatic charge image of the present invention (hereinafter, also simply referred to as "toner") includes a step of aggregating and fusing particles containing resin particles and colorant particles in an aqueous medium. This is a method for producing developing toner.
In the production method, the resin particles are a composite resin having an addition polymerization resin segment which is an addition polymerization of a raw material monomer containing a polyester segment and a styrene compound and a unit derived from a bireactive monomer (hereinafter, simply "composite resin"). Also referred to as "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”).

[In the formula, R ¹ is an alcoholic group having 1 or more and 12 or less carbon atoms, m indicates the average number of substitutions, m has a value of 1 or more and 4 or less, and R ² is a hydrogen atom or 1 or more and 12 carbon atoms. The following alkyl groups, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of moles of alkylene oxide added, and the value of n is 5 or more and 100 or less. , M is ammonium, tetraalkylammonium, or alkali metal. ]
By having such a configuration, it is possible to provide a method for producing a toner for static charge image development, which can obtain a printed matter having a high image density.

The reason why the effect of the present invention can be obtained is not clear, but it is considered as follows.
In the conventional emulsion aggregation method, it has been found that the colorant particles aggregate with each other during aggregation and fusion as one of the factors that reduce the image density of the obtained printed matter of the toner. It was considered that this was because the colorant was not sufficiently stabilized in the binder resin constituting the toner.
In the present invention, as the resin constituting the binder resin, a composite resin A having an addition polymerization resin segment which is an addition polymerization of a polyester segment and a raw material monomer containing a styrene compound and a unit derived from a bireactive monomer is used. Further, a dispersion liquid of the colorant particles obtained by mixing the colorant and the compound 1 having a plurality of aromatic rings in the molecular structure is used in combination. The interaction between the addition-polymerized resin segment of the composite resin A and the aromatic ring of the compound 1 facilitates the dispersal of the colorant particles into the resin particles, and prevents the colorant particles from aggregating during aggregation and fusion. It is presumed that the image density of the printed matter is improved because the dispersibility of the colorant in the toner is improved.

Definitions of various terms in the present 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 of the softening point of the resin to the maximum endothermic peak temperature (softening point (° C.) / maximum endothermic peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins have a crystallinity index of less than 0.6 or more than 1.4. The crystallinity index can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
In the specification, the carboxylic acid component of polyester includes not only the compound but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid. ..

The method for producing a toner for static charge image development of the present invention includes at least a step of aggregating and fusing particles containing resin particles and colorant particles in an aqueous medium, and for example, the following steps may be included. Good.
Step 1: Obtaining composite resin A Step 2: Disperse composite resin A in an aqueous medium to obtain a dispersion of resin particles (hereinafter, also referred to as "resin particles P1") Step 3: Colorant and compound Step 4: Mixing the dispersion liquid containing the resin particles P1 and the dispersion liquid containing the colorant particles Step 5: Step 5: Resin particles P1 and the colorant particles Step 6: Step of fusing the agglomerated particles 1 by aggregating the particles containing the above in an aqueous medium to obtain agglomerated particles (hereinafter, also referred to as “aggregated particles 1”).

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

[Composite resin A]
The composite resin A has a polyester segment, an addition polymerization resin segment which is an addition polymerization 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, it is possible to obtain a toner having excellent low temperature fixability.

(Alcohol component (a-al))
Examples of the alcohol component (a-al) include linear or branched aliphatic diols, aromatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, aromatic diols are preferable, and alkylene oxide adducts of bisphenol A are 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 the ethylene oxide adduct of bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and the propylene oxide adduct of bisphenol A. More preferably, it is a propylene oxide adduct of bisphenol A.

The average number of moles of alkylene oxide adduct 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 even 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% or more in the alcohol component (a-al). It is more than 100 mol%, and more preferably 100 mol% or less.

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, 1, , 12-Dodecanediol.
Examples of the alicyclic diol include hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) and alkylene oxide having 2 or more and 4 or less carbon atoms of hydrogenated bisphenol A (average addition molar number 2 or more and 12). The following) Additives can be mentioned.
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 valent carboxylic acids.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is 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% or more in the carboxylic acid component (a-ac). Below, it is more preferably 70 mol% or less, still more preferably 50 mol% or less.

The linear or branched aliphatic dicarboxylic acid has preferably 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 30 or less, more preferably 20 or less carbon atoms.
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. , Dodecanedioic acid, azelaic 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, and octenyl succinic acid. Of 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 valent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid.
When a trivalent or higher polyvalent carboxylic acid is contained, 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 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 of the carboxy group of the carboxylic acid component (a-ac) to the hydroxyl group of the alcohol component (a-al) [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and It is preferably 1.3 or less, more preferably 1.2 or less.

[Additional polymerization resin segment]
The addition polymer resin segment is an addition polymer of a raw material monomer containing a styrene compound from the viewpoint of obtaining an excellent image density of a printed matter, and is preferably a styrene compound and an aliphatic hydrocarbon having 3 or more and 22 or less carbon atoms. It is an addition polymer of a raw material monomer containing a vinyl-based monomer having a group.

Examples of the styrene-based 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 and the like.
Examples of styrene-based compounds include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. Be done. Of these, styrene is preferable.
The amount of the styrene-based compound is preferably 50% by mass or more, more preferably 55% by mass or more, still more 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, still more preferably 85% by mass or less.

From the viewpoint of further improving the image density of the printed matter, the number of carbon atoms of the hydrocarbon group of the vinyl-based monomer having an aliphatic hydrocarbon group is preferably 3 or more, more preferably 4 or more, still more preferably 6 or more, still more preferably. Is 8 or more, more preferably 10 or more, even more preferably 12 or more, even more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.
By containing a vinyl-based monomer having a long-chain aliphatic hydrocarbon group having 8 or more carbon atoms as a raw material monomer, a microphase-separated structure in the composite resin A can be firmly formed, so that the compound 1 of the colorant particles can be used. It becomes easy to cause the interaction of the colorants, the dispersibility of the colorant is further improved, and the image density is 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 either branched or linear.
The vinyl-based monomer having an aliphatic hydrocarbon group is preferably an alkyl ester of (meth) acrylic acid. In the case of alkyl esters of (meth) acrylic acid, the hydrocarbon group is the alcohol-side residue of the ester.
Examples of the alkyl ester of (meth) acrylic acid include (meth) acrylic acid (iso) propyl, (meth) acrylic acid (iso) butyl, (meth) acrylic acid (iso) hexyl, and (meth) acrylic acid cyclohexyl. (Meta) Acrylic Acid (Iso) Octyl (hereinafter, also referred to as (Meta) Acrylic Acid 2-ethylhexyl), (Meta) Acrylic Acid (Iso) Decyl, (Meta) Acrylic Acid (Iso) Dodecyl (hereinafter, (Meta) Acrylic Examples include acid (iso) lauryl), (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl.
Among these, 2-ethylhexyl (meth) acrylic acid, (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl, (meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) ) Behenyl is preferred, 2-ethylhexyl (meth) acrylic acid, (meth) acrylic acid (iso) dodecyl, (meth) acrylic acid (iso) stearyl are more preferred, (meth) acrylic acid (iso) dodecyl, (meth) Acrylic acid (iso) stearyl is even more preferred, and (meth) acrylic acid (iso) stearyl is even more preferred.
Here, "alkyl (meth) acrylate" means alkyl acrylate or alkyl methacrylate. Further, with respect to the alkyl moiety, "(iso)" means normal alkyl or isoalkyl.

The amount of the vinyl-based monomer having an aliphatic hydrocarbon group having 3 or more and 22 or less 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, 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). ) (Meta) 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-vinylpyrrolidone.

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

[Unit derived from bireactive monomer]
The composite resin A has a unit derived from both reactive monomers from the viewpoint of obtaining an excellent image density of printed matter. When a bireactive monomer is used as the raw material monomer of the composite resin A, the bireactive monomer reacts with the polyester segment, the addition polymerization resin segment, or each of these raw material monomers, and the polyester segment and the addition polymerization resin segment are bonded. It becomes a point.
The "unit derived from a bireactive monomer" means a unit in which a functional group or a vinyl moiety of the bireactive monomer has reacted.
Examples of the bireactive monomer include vinyl-based 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, a vinyl-based monomer having a hydroxyl group or a carboxy group is preferable, and a vinyl-based monomer having a carboxy group is more preferable from the viewpoint of reactivity.
Examples of the bireactive monomer 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 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 parts 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. It is more than a molar part, more preferably 8 mol parts or more, and preferably 30 parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less. When both reactive monomers are used and the amount of each segment in the composite resin A is calculated, the structural unit derived from the bireactive monomers is calculated as being contained 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, still more preferably 55% by mass or more, and 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, 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, and from the viewpoint of further improving the image density of the printed matter. It is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 45% by 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, still more preferably 93% by mass, from the viewpoint of further improving the image density of the printed matter. The above is even 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, still more preferably 100 ° C. or higher, and preferably 140 ° C. or lower, from the viewpoint of further improving the image density of the printed matter. It is preferably 130 ° C. or lower, more preferably 125 ° C. or lower.

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. It is more preferably 60 ° C. or lower, still more preferably 55 ° C. or lower.

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 or more, from the viewpoint of further improving the image density of the printed matter. It is 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 type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate, and these The value is determined by the method described in the examples.
When two or more composite resins A are used in combination, it is preferable that the softening point, the glass transition temperature, and the acid value obtained as a mixture thereof are within the above ranges.

[Method for obtaining composite resin A]
The method for obtaining the composite resin A is, 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 a bireactive monomer of the addition polymerization resin segment. More specifically, the following methods (i) to (iii) can be mentioned.
(I) A method of carrying out an addition polymerization reaction using a raw material monomer and a bireactive monomer of an addition polymerization resin segment after a polycondensation reaction by an alcohol component (a-al) and a carboxylic acid component (a-ac). From the viewpoint, it is preferable that the bireactive monomer is supplied to the reaction system together with the raw material monomer of the addition polymerization resin segment. From the viewpoint of reactivity, catalysts such as an esterification catalyst and an esterification co-catalyst may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be used.
From the viewpoint of further advancing the polycondensation reaction and, if necessary, the reaction with the bireactive monomers, the carboxylic acid component is partially subjected to the polycondensation reaction, then the addition polymerization reaction is carried out, and then the reaction temperature is raised again. It is preferable to add the balance to the reaction system.

It can also be produced by the following method (ii) or (iii).
(Ii) A method of performing an addition polymerization reaction with a raw material monomer of an addition polymerization resin segment and a bireactive monomer followed by a polycondensation reaction with a raw material monomer of a polyester segment (iii) A polycondensation reaction and an addition polymerization with an alcohol component and a carboxylic acid component. Method of Performing Addition Polymerization Reaction with Raw Material Monomer of Resin Segment and Bireactive Monomer in Parallel Both of the polycondensation reaction and addition polymerization reaction of the methods (i) to (iii) above should be carried out in the same container. Is preferable.
The composite resin A is preferably produced by the method (i) or (ii) above because of the high degree of freedom in the reaction temperature of the polycondensation reaction, and the above (i) is more preferable.

In the polycondensation reaction, the alcohol component (a-al) and the carboxylic acid component (a-ac) are polycondensed. If necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, and titanium diisopropirate bistriethanol aminated is added to the total amount of 100 parts by mass of the alcohol component and the carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less; an esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) is added to 100 parts by mass in total of the alcohol component and the carboxylic acid component. On the other hand, 0.001 part by mass or more and 0.5 part by mass or less; further, if necessary, a radical polymerization inhibitor such as 4-tert-butylcatechol was added by 0.001 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Polycondensation may be carried out by using more than 25 parts by mass or less.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 230 ° C. or lower.
The polycondensation may be carried out in an inert gas atmosphere.

In the addition polymerization reaction, the raw material monomer and the bireactive monomer of the addition polymerization resin segment are addition-polymerized.
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. Further, 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). Known radical polymerization initiators of the above 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. It is preferably 15 parts by mass or less.

<Process 2>
Step 2 is a step of dispersing the composite resin A in an aqueous medium to obtain a dispersion liquid of the resin particles P1.
Here, in addition to the composite resin A, a resin that can be used for other toners, such as 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, still more preferably 95% by mass or more in the resin components constituting the resin particles P1 from the viewpoint of obtaining an excellent image density of the printed matter. , More preferably 98% by mass or more, and preferably 100% by mass or less, even more preferably 100% by mass.
The amount of the resin component in the resin particles 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% by mass. It is mass% or less, more preferably 100 mass%.
Examples of the method for obtaining the dispersion liquid of the resin particles P1 include a method in which the composite resin A is added to an aqueous medium and a dispersion treatment is performed by a disperser or the like, or an aqueous medium is gradually added to an organic solvent solution of the composite resin A. A method of phase inversion emulsification can be mentioned, but a method of phase inversion emulsification is preferable.

≪Aqueous medium≫
The aqueous medium preferably contains water as a main component, and the content of water in the aqueous medium is preferably 80% by mass from the viewpoint of improving the dispersion stability of the dispersion liquid of the resin particles and from the viewpoint of environmental friendliness. % 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, still more preferably 100% by mass. As the water, deionized water or distilled water is preferable.
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 soluble in water such as cyclic ethers such as tetrahydrofuran. Organic solvent to be used.
Among these, from the viewpoint of preventing the organic solvent from being mixed into the toner, an alkyl alcohol having 1 or more and 5 or less carbon atoms that does not dissolve polyester is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

[Phase inversion emulsification]
Examples of the phase inversion emulsification method include a method of preparing an organic solvent solution of the composite resin A and then adding an aqueous medium to the obtained solution for phase inversion emulsification, and adding an aqueous medium to the melted composite resin A. Then, there is a method of inversion emulsification. The former method is preferable from the viewpoint of obtaining a dispersion liquid of homogeneous resin particles P1.

Organic solvents, solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc) when expressed in, preferably 15.0 MPa ^1/2 or more, more preferably 16.0MPa ^1/2 or more, It is more preferably 17.0 MPa ^1/2 or more, preferably 26.0 MPa ^1/2 or less, more preferably 24.0 MPa ^1/2 or less, still more preferably 22.0 MPa ^1/2 or less.
Examples of the organic solvent include alcohol solvents such as ethanol (26.0), isopropanol (23.5) and isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0) and 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), dioxane (20.5); ethyl acetate ( Examples thereof include acetate-based solvents such as 18.6) and isopropyl acetate (17.4). The numerical value in parentheses after each solvent is each SP value (unit: MPa ^1/2 ). Among these, at least one selected from a ketone solvent and an acetate ester solvent is preferable, and at least one selected from methyl ethyl ketone, ethyl acetate and isopropyl acetate is preferable from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium. Species are more preferred, and methyl ethyl ketones are even more preferred.

The concentration of the resin in the organic solvent solution is preferably 20% by mass or more, more preferably 40% 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 hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; and 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, an alkali metal hydroxide is preferable, and sodium hydroxide is more preferable.

The equivalent amount (mol%) of the neutralizing agent to the acid group 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 100 mol% or less.
The equivalent amount (mol%) of the neutralizing agent used can be calculated by the following formula. When the equivalent amount of the neutralizing agent is 100 mol% or less, it is synonymous with the degree of neutralization. When the equivalent amount of the neutralizing agent used exceeds 100 mol%, the neutralizing agent is the acid group of the resin. The degree of neutralization of the resin at this time is considered to be 100 mol%.
Equivalent to use of neutralizer (mol%) = [{Equivalent mass of neutralizer (g) / Equivalent of neutralizer} / [{Weighted average acid value of resin constituting resin particles P1 (mgKOH / g) × Mass of resin constituting resin particles P1 (g)} / (56 × 1000)]] × 100

The amount of the aqueous medium to be added is preferable with respect to 100 parts by mass of the resin constituting the resin particles P1 from the viewpoint of improving the dispersion stability of the resin particles 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, further 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 (aqueous medium / organic solvent) of the aqueous medium to the organic solvent is preferably 20/80 or more, more preferably 50/50 or more, and further. It is preferably 60/40 or more, preferably 97/3 or less, more preferably 93/7 or less, and even 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, further preferably 70 ° C. or higher, and preferably 85 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 75 ° C. or higher. It is below ° C.

From the viewpoint of obtaining resin particles having a small particle size, the addition rate of the aqueous medium is preferably 0.1 part by mass or more with respect to 100 parts by mass of the resin constituting the resin particles until the phase inversion is completed. It is 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. It is less than a part / minute. There is no limit to the rate of addition of the aqueous medium after phase inversion.

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

The solid content concentration of the dispersion liquid of the resin particles P1 is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less. It is 0% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The solid content is the total amount of non-volatile components such as resin, colorant, and surfactant.

The volume median particle diameter 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 0.08 μm or more, 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 0.30 μm or less.
Here, the volume medium particle size D ₅₀ is a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size, and is described in 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, still more preferably, from the viewpoint of improving the productivity of the dispersion liquid of the resin particles P1. It is 15% or more, and is preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, from the viewpoint of obtaining a toner that can obtain a high-quality image.
The CV value is a value represented by the following formula. The volume average particle size in the following formula is the particle size obtained by multiplying the particle size measured on a volume basis by the ratio of particles having that particle size value and dividing the value obtained thereby by the number of particles. is there. The CV value is determined by the method described in Examples.
CV value (%) = [standard deviation of particle size distribution (μm) / volume average particle size (μm)] × 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 antiaging agent as long as the effects of the present invention are not impaired.

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

≪Colorant≫
Pigments and dyes are used as the colorant, and pigments are preferable from the viewpoint of improving the image density of the toner. As the pigment, either an inorganic pigment or an organic pigment can be used, but an organic pigment is preferable.
Examples of the inorganic pigment include carbon black and an inorganic composite oxide.
As the organic pigment, a yellow pigment, a magenta pigment, a cyan pigment and the like are used.
Examples of magenta organic pigments include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, base dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. 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. Pigment Bio Red 19 can be mentioned. Among these, naphthol compounds are preferable, and C.I. I. Pigment Red 269 is more preferred.

Examples of the cyan organic pigment include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. More specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. Among these, copper phthalocyanine compounds are preferable, and C.I. I. Pigment Blue 15: 3 is more preferred.

Examples of the yellow organic pigment include monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, isoindolin 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. Among these, monoazo compounds are preferable, and C.I. I. Pigment Yellow 74 is more preferred.
Examples of the dye include acridine-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, indigo-based, phthalocyanine-based, and aniline black-based dyes.
The colorants can be used alone or in combination of two or more.
The content of the colorant in the colorant particles 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% by mass or less. It is mass% or less, more preferably 80 mass% or less.

≪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.

[In the formula, R ¹ is an alcoholic group having 1 or more and 12 or less carbon atoms, m indicates the average number of substitutions, m has a value of 1 or more and 4 or less, and R ² is a hydrogen atom or 1 or more and 12 carbon atoms. The following alkyl groups, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of moles of alkylene oxide added, and the value of n is 5 or more and 100 or less. , M is ammonium, tetraalkylammonium, or alkali metal. ]

R ¹ is preferably an alkanediyl group having 1 or more and 4 or less carbon atoms, and more preferably an alkanediyl group having 1 or more and 2 or less carbon atoms. The plurality of R ¹ may or may the same or different and are preferably the same.
Examples of R ¹ include a methanediyl group (also referred to as a methylene group), an ethane-1,1-diyl group, and an ethane-1,2-diyl group (these are "ethanediyl groups" or "ethylene groups" as a comprehensive concept. (Also also called), propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,1-diyl group, butane-1,2-diyl group, butane. Examples thereof include -1,3-diyl group, butane-1,4-diyl group, and butane-2,3-diyl group. Among these, a methanediyl group and an ethanediyl group are preferable, and an ethanediyl group is more preferable.
The value of m is preferably 2 or more and 3 or less.
When R ¹ is a methanediyl group, the value of m is preferably 2 or more and 3 or less, more preferably 3.
When R ¹ is an ethanediyl group, the value of m is preferably 1 or more and 2 or less, more preferably 2.
R ² is preferably a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
A ¹ preferably contains an ethylene group, or an ethylene group and a propylene group, and is more preferably an ethylene group.
The value of n is preferably 6 or more, more preferably 9 or more, still more preferably 11 or more, even more preferably 12 or more, and preferably 50 or less, more preferably 30 or less, still more preferably 20 or less. Even more preferably, it is 15 or less.
M is preferably ammonium, an alkali metal, and more preferably ammonium.

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

[In the formula, R ¹ is a methanediyl group or an ethanediyl group, m indicates the average number of substitutions, the value of m is 2 or more and 3 or less, EO is an oxyethylene group, and n is the average of alkylene oxides. It is the number of added moles, the value of n is 6 or more and 30 or less, and M is ammonium. ]

Examples of the compound 1 include polyoxyethylene distyrene phenyl ether monosulfate ammonium salt, polyoxypropylene polyoxyethylene distyrene phenyl ether monosulfate ammonium salt, and polyoxyethylene tribenzylphenyl ether sulfate ammonium salt. Can be mentioned.
Among these, from the viewpoint of improving the image density of printed matter, polyoxyethylene distyrene phenyl ether monosulfate ester ammonium salt, polyoxyethylene tribenzylphenyl ether sulfate ester ammonium salt, and more preferably polyoxyethylene distyrene. Benzyl ether monosulfate ammonium salt. The average number of moles of these polyoxyethylene groups added is preferably in the range of n described above.

Compound 1 can be obtained by a known method. For example, in step A1 of reacting a phenolic compound with a basic substance and an alkylene oxide at 100 ° C. or higher and 160 ° C. or lower to obtain a polyoxyalkylene phenyl ether compound. , A method comprising a step A2 of dehydrating and condensing a polyoxyalkylene phenyl ether compound with sulfamic acid or sulfuric acid.

When the colorant and the compound 1 are mixed, 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. It is more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably 40 parts by mass or less.

In the mixing of the colorant and the compound 1 in the step 3, for example, the colorant, the compound 1, and the aqueous medium are preferably mixed using a disperser to disperse the colorant. By dispersing the colorant with the compound 1 to obtain the colorant particles, the affinity between the colorant and the composite resin A is enhanced during aggregation and fusion, and the image density of the printed matter can be further improved. ..
Examples of the disperser include a homomixer, a homogenizer, and an ultrasonic disperser. Commercially available products of suitable dispersers include, for example, a homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), a high-pressure homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics), and an ultrasonic machine. An example of the ultrasonic homogenizer "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.).

The solid content concentration of the dispersion liquid of the colorant 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 from the viewpoint of improving the productivity of the toner. Is 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.

The volume median particle diameter D ₅₀ of the colorant particles in the dispersion 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 0.30 μm or less, still more preferably 0.25 μm or less.
The CV value of the colorant particles in the dispersion 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, further. It is preferably 35% or less.

<Step 4>
Step 4 is a step of mixing the dispersion liquid containing the resin particles P1 and the dispersion liquid 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, still more 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. It is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.
The mass ratio of the colorant to the composite resin A [colorant / composite resin A] is preferably 3/97 or more, more preferably 5/95 or more, still more preferably 8/92 or more, and preferably It is 85/15 or less, more preferably 70/30 or less, still more preferably 50/50 or less, still more preferably 30/70 or less.
In step 4, for example, a dispersion liquid of resin particles other than the resin particles P1 and, if necessary, a dispersion liquid of wax particles are added.

≪Dispersion of wax particles≫
(wax)
Examples of the wax include hydrocarbon wax, ester wax, silicone wax, and fatty acid amide wax.
Examples of the hydrocarbon wax include minerals such as paraffin wax and Fishertropsh wax or petroleum-based hydrocarbon wax; synthetic hydrocarbon wax such as polyolefin wax such as polyethylene wax, polypropylene wax and polybutene wax.
Examples of the ester wax include minerals such as Montan wax or petroleum-based ester wax; plant-based ester wax such as carnauba wax, rice wax and candelilla wax; and animal-based ester wax 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, hydrocarbon wax or ester wax is preferable, hydrocarbon wax is more preferable, and at least one selected from paraffin wax, Fishertroph wax, and polyolefin wax is more preferable, and paraffin. Wax is even more preferred.

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, still more preferably 85 ° C. or lower.
The melting point of the wax is determined by the method described in the examples.

From the viewpoint of toner releasability, the amount of 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. Yes, and from the viewpoint of suppressing desorption and exposure of the wax at the time of aggregation and fusion, it is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.

The dispersion liquid of the wax particles can be obtained by using a surfactant, but the wax and the resin particles P _W described later can be mixed and obtained by desorbing and exposing the wax at the time of aggregation and fusion. It is preferable from the viewpoint of suppressing.

(Resin particles P _W )
The resin constituting the resin particles P _W is not particularly limited, but is preferably a polyester resin, and from the viewpoint of improving the dispersibility of the wax in the aqueous medium, the composite resin Aw having a polyester segment and an addition polymerization resin segment. Is more preferable to use.
The composite resin Aw is preferably an amorphous resin.
As the composite resin Aw, the composite resin exemplified in the above-mentioned 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 in the composite resin A.
The dispersion liquid of the resin particles P _W can be obtained, for example, by the above-mentioned phase inversion emulsification method. The specific conditions and procedures of phase inversion emulsification, that is, the aqueous medium to be used, the components other than water that can constitute the aqueous medium, the amount of the aqueous medium, the addition temperature, and the addition rate are also applied to the above-mentioned items described in step 2. Can be done.

The solid content concentration of the dispersion liquid of the resin particles P _W 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 P _W is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more, and preferably 50% or less. It is more preferably 40% or less, still more preferably 30% or less.

(Manufacturing of dispersion of wax particles)
The dispersion liquid of the wax particles is obtained by mixing the wax and the dispersion liquid of the resin particles P _W.
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 dispersion liquid of the wax particles has a structure in which a large number of resin particles P _W are adsorbed around the wax particles. As a result, the wax particles are easily incorporated into the aggregate of the resin particles P1 in the subsequent agglutination step.

The dispersion liquid of the wax particles is obtained, for example, by dispersing the wax, the dispersion liquid of the resin particles P _W , and, if necessary, the aqueous medium at a temperature equal to or higher than the melting point of the wax using a disperser. The disperser is preferably a homogenizer, a high-pressure disperser, an ultrasonic disperser, or the like, and more preferably an ultrasonic disperser, from the viewpoint of the stability of the wax particles. The dispersion time may be appropriately set depending on the disperser used. Examples of the ultrasonic disperser include an ultrasonic homogenizer. Commercially available ultrasonic homogenizers include, for example, "US-150T", "US-300T", "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.), "SONIFIER (registered trademark) 4020-400", and "SONIFIER". (Registered Trademark) 4020-800 ”(manufactured by Branson).
Further, before using the disperser, the wax, the dispersion liquid of the resin particles P _W , and if necessary, the aqueous medium may be pre-dispersed in advance with a mixer such as a homomixer or a ball mill. A preferred embodiment of the aqueous medium is the same as that used for 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 further 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. It is more preferably 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, still more preferably 50 parts by mass or less.

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

It is preferable that the wax and the dispersion liquid of the resin particles P _W are added to the aqueous medium and dispersed while being heated at a temperature equal to or higher than the melting point of the wax.
The heating temperature at the time of dispersion is preferably equal to or higher than the melting point of the wax and 80 ° C. or higher, more preferably 85 ° C. or higher, still more preferably 90 ° C. or higher, and preferably 90 ° C. or higher, from the viewpoint of improving the productivity of the wax particle dispersion liquid. Is less than the softening point of the resin contained in the resin particles P _W and is 100 ° C. or lower, more preferably 98 ° C. or lower, still more preferably 95 ° C. or lower.

The solid content concentration of the dispersion liquid of the 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 more. % Or less, more preferably 25% by mass or less.
Volume-median particle size _{D 50} of the wax particles is preferably 0.05μm or more, more preferably 0.20μm or more, more preferably at least 0.40 .mu.m, and preferably 1.00μm or less, more preferably 0 It is .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, still more preferably 10 or less, from the viewpoint of improving the dispersion stability of the 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 controlling aggregation in the next step 5 to obtain aggregated particles having a target particle size. It is more preferably 12% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.
The mass ratio of the wax particles to the resin particles P1 in the mixed dispersion [wax particles / resin particles P1] is preferably 0.05 or more, more preferably 0.10 or more, and preferably 1.0 or less. It is more preferably 0.5 or less, still more preferably 0.2 or less.
The mixing temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, and preferably 40 ° C. or lower, from the viewpoint of controlling aggregation to obtain agglomerated particles having a desired particle size. , More preferably 30 ° C. or lower.

When preparing the mixed dispersion, it may be carried out in the presence of a surfactant from the viewpoint of improving the dispersion stability of arbitrary components such as resin particles P1 and wax particles added as needed.
As the surfactant, for example, anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates, nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers, and the like can be used.
When a surfactant is used, the amount used is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the resin particles P1. It is less than or equal to parts by mass, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.

<Step 5>
Step 5 is a step of aggregating the particles containing the resin particles P1 and the colorant particles in an aqueous medium to obtain the agglomerated particles 1. In this step, the flocculant may be further mixed in an aqueous medium.
Step 5 may include the next step 5A, followed by step 5B.
Step 5A: Particles containing resin particles P1 and colorant particles are agglomerated in an aqueous medium preferably in the presence of wax particles to obtain agglomerated particles 1c. Step 5B: Agglomerated particles 1c are combined with a resin (hereinafter, "resin"). A step of adding resin particles P2 containing (also referred to as "As") to obtain aggregated particles 1cs formed by adhering resin particles P2. The aggregated particles 1 are higher ranks including the aggregated particles 1c and the aggregated particles 1cs. Used in the sense of concept.

<Step 5A>
The agglomerated particles 1c are obtained by mixing an optional component such as an aggregating agent and a surfactant with a dispersion of resin particles P1, colorant particles, and if necessary, wax particles, and aggregating them.

≪Coagulant≫
The flocculant is used from the viewpoint of efficiently performing flocculation.
Examples of the flocculant include a cationic surfactant for a quaternary salt, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as an inorganic metal salt, an inorganic ammonium salt, and a divalent or higher metal complex. .. From the viewpoint of improving the cohesiveness and obtaining uniform agglomerated particles, an inorganic flocculant having a valence of 1 or more and 5 or less is preferable, an inorganic metal salt having a valence or more and a divalent or less, an inorganic ammonium salt is more preferable, and an inorganic ammonium salt is preferable. More 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, ammonium sulfate is more preferable as the flocculant.
The flocculant is preferably added dropwise as an aqueous solution of the flocculant in an amount of 2% by mass or more and 40% by mass or less from the viewpoint of controlling aggregation to obtain aggregated particles having a desired particle size. The pH of the aqueous solution of the flocculant is preferably 7.0 or more and 9.0 or less.

Using a flocculant, for example, 5 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the total amount of resin in a mixed dispersion containing resin particles P1 at 0 ° C. or higher and 40 ° C. or lower (preferably 20 ° C. or higher and 30 ° C. or lower) 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 agglomerated in an aqueous medium to obtain agglomerated 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 raise the temperature of the dispersion after adding the aggregating agent. 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.

The volume median particle diameter D ₅₀ of the agglomerated 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, still more preferably 6 μm or less. Is. The volume median particle diameter of the agglomerated particles is determined by the method described in Examples described later.

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

By passing through the agglomerated particles 1cs, a toner particle having a core-shell structure in which the component of the agglomerated particles 1c is contained in the core portion and the resin As is contained in the shell portion 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)
As the resin As, polyester which is a polycondensate of an alcohol component (as-al) and a carboxylic acid component (as-ac) is preferable. The resin As is preferably an amorphous resin.
An example of the alcohol component (as-al) and the carboxylic acid component (as-ac) is omitted because it is common to the alcohol component (a-al) and the carboxylic acid component (a-ac) of the composite resin A. The following aspects are preferable as the resin As.

The softening point of the resin As is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, further 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, 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 heat-resistant storage stability, and from the viewpoint of improving low-temperature fixability. It is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, and even more preferably 70 ° C. or lower.

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 more, from the viewpoint of improving the dispersion stability of the resin particles P2. / G or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

As a method for obtaining the dispersion, a method of gradually adding an aqueous medium to an organic solvent solution of the resin or the like and emulsifying the phase inversion is preferable 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 in which an aqueous medium is added 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 the organic solvent that can be used are also the same as those of the aqueous medium and the 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 rate of the aqueous medium are the same as the method for producing the resin particles P1.

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

The amount of the resin particles P2 added 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, still more 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 medium particle size D ₅₀ of the agglomerated 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 that can obtain a high-quality image. Hereinafter, it is more preferably 9 μm or less, still more preferably 8 μm or less.

In step 5, the agglomeration may be stopped when the agglomerated particles have grown to an appropriate particle size as toner.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation inhibitor, a method of diluting the dispersion, and the like. From the viewpoint of surely preventing unnecessary aggregation, a method of adding an aggregation terminator to stop aggregation is preferable.

≪Coagulation terminator≫
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, polyoxyalkylene alkyl ether sulfates and the like.
The aggregation terminator can be used alone or in combination of two or more.

The amount of the aggregation terminator added is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the resin in the toner, from the viewpoint of surely preventing unnecessary aggregation. It is more preferably 2 parts by mass or more, and from the viewpoint of reducing the residue on the toner, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 7 parts by mass or less. The aggregation terminator may be added in 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 aggregated particles is held from the viewpoint of improving the productivity of the toner. The temperature is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, further preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.
Further, from the viewpoint of stabilizing the agglomerated particles and preventing the once agglomerated particles from being dispersed before fusion, it is preferable to stop the agglomeration and add an acid to make the dispersion liquid of the agglomerated 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. However, from the viewpoint of rapid pH change with respect to addition, hydrochloric acid, hydrochloric acid, nitric acid, and acetic acid are preferable. At least one selected from, more preferably at least one selected from hydrochloric acid, sulfuric acid, and nitric acid, still more preferably sulfuric acid.
The acid is preferably added in the form of an aqueous solution. It may also be added together with an aggregation terminator.

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

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

Volume-median particle size _{D 50} of the fused particles is preferably 2μm or more, more preferably 3μm or more, still more preferably 4μm or more, and, preferably 10μm or less, more preferably 8μm or less, more preferably 6μm or less 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-treatment process>
A post-treatment step may be performed after the step 6, and it is preferable to obtain the toner particles by isolating the fused particles from the dispersion obtained in the step 6.
Since the fused particles in the dispersion liquid obtained in step 6 are present in the aqueous medium, it is preferable to first perform solid-liquid separation. A suction filtration method or the like is preferably used for solid-liquid separation.
It is preferable to perform cleaning after solid-liquid separation. At this time, since it is preferable to remove the added surfactant as well, 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 temperature at the time of drying is preferably such that the temperature of the fused particles themselves is lower than the minimum value of the 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 fluid 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.
Toner particles can be obtained by drying the fused particles.

As the post-treatment step, there may be a step of mixing the toner particles and the external additive.
Examples of the external additive include hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Of these, hydrophobic silica is preferred.
When an 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, still more preferably 3 parts by mass or more with respect to 100 parts by mass of the toner particles, and It is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and further preferably 4 parts by mass or less.

[Toner for static charge image development]
<Toner particles>
The toner particles obtained by the above method can be used as they are as the toner for static charge image development, but it is preferable to use the toner particles whose surface is treated as described above as the toner for static charge image development.

Volume-median particle size D ₅₀ of the toner particles, from the viewpoint of obtaining a high quality image, preferably 2μm or more, more preferably 3μm or more, still more preferably 4μm or more, and, preferably 10μm or less, more preferably It is 8 μm or less, more preferably 6 μm or less.
The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, further preferably 16% or more, and preferably 30% or less, more preferably 26, from the viewpoint of obtaining a high-quality image. % Or less.
The circularity of the toner particles is preferably 0.955 or more, more preferably 0.960 or more, still more preferably 0.965 or more from the viewpoint of obtaining a high-quality image, and from the viewpoint of toner cleanability. It is preferably 0.990 or less, more preferably 0.985 or less, and further preferably 0.980 or less.

Toner is used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. In addition, the toner can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

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

[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.

[Resin softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C./min while a load of 1.96 MPa is applied by a plunger to give a diameter of 1.96 MPa. Extruded from a 1 mm, 1 mm long nozzle. 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 used as the softening point.
(2) Crystallinity index 0.02 g of a sample is weighed in an aluminum pan using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), and the temperature drops from room temperature (25 ° C) to 10 ° C / It was cooled to 0 ° C. in min. Then, the sample was allowed to stand still for 1 minute, and then the temperature was raised to 180 ° C. at a heating rate of 10 ° C./min to measure the amount of heat. Of the observed endothermic peaks, the temperature of the peak with the largest endothermic area is set as the maximum endothermic peak temperature (1), and (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)). The crystallinity index was calculated.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample is weighed in an aluminum pan, heated to 200 ° C, and the temperature thereof. The temperature was lowered to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the temperature of the sample was raised at a heating rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the largest peak area was defined as the maximum endothermic peak temperature (2). In the case of crystalline resin, the peak temperature was taken as the melting point.
In the case of amorphous resin, when a peak is observed, the temperature of the peak is observed, and when a step is observed without a peak, a tangent line indicating the maximum inclination of the curve of the step portion and the step The temperature at the intersection with the extension of the baseline 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.), weigh 0.02 g of a sample into an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from 200 ° C to 10 ° C / min. Was cooled to 0 ° C. Next, the sample was heated at a heating rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endothermic reaction was taken as the melting point.

[Resin particles, colorant particles, and the volume-median particle size D ₅₀ and CV value of the wax particles]
(1) Measuring device: Laser diffraction type particle size measuring machine "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) x 100

[Solid concentration of resin particle dispersion, colorant particle dispersion, and wax particle dispersion]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), 5 g of the measurement sample was dried at a drying temperature of 150 ° C. ), The water content (% by mass) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (mass%) = 100-moisture (mass%)

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

[Volume-median particle size _{D 50} and CV value of the 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 "Emargen (registered trademark) 109P" [manufactured by Kao Corporation, HLB (Hydrophile-Lipopfile Balance) = 13.6] is dissolved in the electrolytic solution to prepare a dispersion having a concentration of 5% by mass. Obtained.
Dispersion conditions: 10 mg of a sample to be measured of toner particles after drying is added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution is added, and further, with an ultrasonic disperser. A sample dispersion was prepared by dispersing for 1 minute.
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size is measured. It was determined volume median particle diameter D ₅₀ and a volume average particle size from distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) x 100

[Image density of printed matter]
First, the following fixing test was performed to set the minimum fixing temperature.
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhered to the paper is 1.48 to 1. A solid image of .52 mg / cm ² was output with a length of 50 mm without fixing, leaving a margin of 5 mm from the upper end of the A4 paper.
Next, the same printer in which the fuser was modified to have a variable temperature was prepared, the temperature of the fuser was set to 110 ° C., and toner was fixed at a speed of 1.2 seconds per sheet in the A4 vertical direction to obtain a printed matter.
In the same manner, the temperature of the fuser was raised by 5 ° C. to fix the toner, and a printed matter was obtained.
From the top margin of the printed matter to the solid image, lightly paste the mending tape "Scotch (registered trademark) Mending Tape 810" (manufactured by Sumitomo 3M Ltd., width 18 mm) cut to a length of 50 mm. After that, a weight of 500 g was placed and pressed back and forth at a speed of 10 mm / s. Then, the attached tape was peeled off from the lower end side at a peeling angle of 180 ° and a speed of 10 mm / s to obtain a printed matter after the tape was peeled off. 30 sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) are laid under the printed matter before and after the tape is applied, and the reflected image density of the fixed image part before and after the tape is applied to each printed matter is measured. , Colorimeter "SpectroEye" (manufactured by GretagMacbeth, light irradiation conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and the fixation rate from each reflected image density according to the following formula. Was calculated.
Fixing rate (%) = (reflection image density after tape peeling / reflection image density before tape application) x 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 Corporation) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhered to the paper was 0. A solid image of 35 mg / cm ² was output.
The temperature of the fuser was set to the minimum fixing temperature + 10 ° C. obtained in the fixing test, and the toner was fixed in the A4 longitudinal direction at a speed of 1.2 seconds per sheet to obtain a printed matter.
30 sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) are laid under the printed matter, and the reflected image density of the solid image part of the output printed matter is measured by the colorimeter "SpectroEye" (manufactured by GretagMacbeth). Irradiation conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard) were used for measurement, and the measured values of any 10 points on the image were averaged to obtain the image density. The larger the value, the better the image density.

[Manufacturing of resin (including step 1)]
Manufacturing example A1
(Manufacturing of composite resin A-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced 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. with stirring under a nitrogen atmosphere, and 5 at 235 ° C. After holding for a time, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 2198 g of styrene, 550 g of stearyl methacrylate, 109 g of acrylic acid, and 330 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 241 g of fumaric acid, 572 g of sebacic acid, 181 g of trimellitic acid anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr to 210 ° C. Then, the reaction was carried out at 4 kPa to a desired softening point to obtain a composite resin A-1. The physical properties are shown in Table 1.

Production Examples A2 to A5
(Manufacturing 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
(Manufacturing of resin A-6)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced 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. with stirring under a nitrogen atmosphere, and 8 at 235 ° C. After holding for a time, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 197 g of fumaric acid, 1404 g of sebacic acid, 296 g of trimellitic acid anhydride, and 3.8 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr to 220 ° C. After that, the pressure in the flask was lowered, and the reaction was carried out at 10 kPa to a desired softening point to obtain resin A-6. The physical properties are shown in Table 1.

Manufacturing example A7
(Manufacturing of resin A-7)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 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. with stirring under a nitrogen atmosphere, and 5 at 235 ° C. After holding for a time, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 2197 g of styrene, 549 g of stearyl methacrylate, and 330 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 330 g of fumaric acid, 574 g of sebacic acid, 182 g of trimellitic acid anhydride, and 3.5 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr to 210 ° C. Then, the reaction was carried out at 4 kPa to a desired softening point to obtain resin A-7. The physical properties are shown in Table 1. Two glass transition temperatures were observed for resin A-7.

Manufacturing example A8
(Manufacturing of composite resin A-8)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced 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 under a nitrogen atmosphere. After holding at 235 ° C. for 5 hours, the pressure in the flask was reduced and the flask was held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 2756 g of styrene, 689 g of stearyl methacrylate, 142 g of acrylic acid, and 413 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding the temperature 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 a desired softening point to obtain a composite resin A-8. The physical properties are shown in Table 1.

[Manufacturing of resin particle dispersion (step 2)]
Manufacturing example X1
(Manufacture of Resin Particle Dispersion Liquid 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 container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube, and 2 at 73 ° C. The resin was dissolved over time. A 5 mass% aqueous sodium hydroxide solution was added to the obtained solution so as to have a neutralization degree of 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. Methyl ethyl ketone was distilled off under reduced pressure while the temperature was continuously maintained at 73 ° C. to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid X-1 was obtained. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 2.

Production example X2 to X7
(Manufacturing of resin particle dispersion liquids X-2 to X-7)
Resin particle dispersion liquids 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. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 2.

Production example Y1
(Manufacture of Resin Particle Dispersion Liquid Y-1)
200 g of composite resin A-8 and 200 g of methyl ethyl ketone were placed in a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube, and the resin was dissolved at 73 ° C. for 2 hours. I let you. A 5 mass% aqueous sodium hydroxide solution was added to the obtained solution so as to have a neutralization degree of 60 mol% with respect to the acid value of the composite resin A-8, and the mixture was stirred for 30 minutes.
Then, 700 g of deionized water was added over 50 minutes while stirring at 280 r / min (peripheral speed 88 m / min) while maintaining the temperature at 73 ° C. for phase inversion emulsification. Methyl ethyl ketone was distilled off under reduced pressure while the temperature was continuously maintained at 73 ° C. to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid Y-1 was obtained. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 2.

[Manufacturing of dispersant]
Production example C1
(Synthesis of dispersant C-1 (polyoxyethylene (13) distyrene phenyl ether monosulfate ammonium salt))
(Step A1)
608 g (2 mol) of distyrene phenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 0.56 g (0.01 mol) of potassium hydroxide were placed in an autoclave equipped with a stirrer, a temperature control device and an ethylene oxide introduction device at 110 ° C. , 1.3 kPa for 30 minutes. Then, nitrogen substitution was performed, the temperature was raised to 145 ° C., and then 1144 g (26 mol) of ethylene oxide was charged. An addition reaction was carried out at 145 ° C. until the pressure became constant, aging was carried out at 145 ° C. for 1 hour, and then the mixture was cooled to 80 ° C. Next, potassium hydroxide was removed by adding an inorganic alkali adsorbent and filtering to obtain polyoxyethylene (13) distyreneated phenol having an average addition mole number of ethylene oxide of 13 mol (however, however). The numbers in parentheses indicate the average number of moles of ethylene oxide added; the same applies below).
(Step A2)
438.0 g (0.5 mol) of this polyoxyethylene (13) distyrene phenol was charged into a reactor equipped with a stirrer and a temperature control device, and water was removed at 110 ° C. and 1.3 kPa for 30 minutes. .. After cooling to 80 ° C., 46.1 g (0.475 mol) of sulfamic acid was charged, the temperature was raised to 110 ° C., and the mixture was reacted for 3 hours to polyoxyethylene (13) distyrene phenyl ether monosulfate ammonium salt (dispersant). C-1) was obtained.

Production example C2
(Synthesis of dispersant C-2 (polyoxyethylene (20) distyrene phenyl ether monosulfate ammonium salt))
The amount of ethylene oxide charged in step A1 was changed from 1144 g (26 mol) to 1760 g (40 mol), and in step A2, the amount of polyoxyethylene distyreneated phenol obtained in step A1 was changed to 0.5 mol. Dispersant C-2 was obtained in the same manner as in Production Example C1 except that the mass was adjusted to be moderate.

Production example C3
(Synthesis of dispersant C-3 (polyoxypropylene (3) polyoxyethylene (10) distyrene phenyl ether monosulfate ammonium salt))
(Step A1)
608 g (2 mol) of distyrene phenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 0.56 g (0.01 mol) of potassium hydroxide were placed in an autoclave equipped with a stirrer, a temperature control device and an ethylene oxide introduction device at 110 ° C. , 1.3 kPa for 30 minutes. Then, nitrogen substitution was performed, the temperature was raised to 120 ° C., and then 348 g (6 mol) of propylene oxide was charged. The addition reaction was carried out at 120 ° C. until the pressure became constant, and after aging at 120 ° C. for 1 hour, water was removed at 110 ° C. and 1.3 kPa for 30 minutes. Then, nitrogen substitution was performed, the temperature was raised to 145 ° C., and then 880 g (20 mol) of ethylene oxide was charged. The addition reaction was carried out at 145 ° C. until the pressure became constant, and after aging at that temperature for 1 hour, the mixture was cooled to 80 ° C. Next, potassium hydroxide was removed by adding an inorganic alkali adsorbent and filtering, and polyoxypropylene (3) having an average addition mole number of 3 mol of propylene oxide and an average addition mole number of 10 mol of ethylene oxide. ) Polyoxyethylene (10) distyreneated phenol was obtained.
(Step A2)
This polyoxypropylene (3) polyoxyethylene (10) distyrene phenol 459.0 g (0.5 mol) was charged into a reactor equipped with a stirrer and a temperature control device, and charged at 110 ° C. and 1.3 kPa for 30 minutes. Moisture was removed. After cooling to 80 ° C., 46.1 g (0.475 mol) of sulfamic acid was charged, the temperature was raised to 110 ° C., and the reaction was carried out for 3 hours to polyoxypropylene (3) polyoxyethylene (10) distyrene phenyl ether monosulfate. An ester ammonium salt (dispersant C-3) was obtained.

Production example C4
(Synthesis of Dispersant C-4: Polyoxyethylene (10) Tribenzylphenyl Ether Sulfate Ammonium Salt)
In step A1, 608 g (2 mol) of distyrene phenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was changed to 592 g (2 mol) of tribenzylphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.), and 1144 g (26 mol) of ethylene oxide was used. Was changed to 880 g (20 mol), and further, in step A2, the polyoxyethylene tribenzylphenol obtained in step A1 was adjusted to a mass of 0.5 mol, but the same as Production Example C1. Similarly, dispersant C-4 was obtained.

Production example C5
(Synthesis of Dispersant C-5: Polyoxyethylene (7) Distyreneized (Methyl) Phenyl Ether Monosulfate Ammonium Salt)
313.0 g (0.5 mol) of polyoxyethylene (7) distyreneated methylphenol (manufactured by Nippon Emulsifier Co., Ltd.) was charged into a reactor equipped with a stirrer and a temperature control device, and 30 at 110 ° C. and 1.3 kPa. Moisture was removed for minutes. After cooling to 80 ° C., 46.1 g (0.475 mol) of sulfamic acid was charged, the temperature was raised to 110 ° C., and the reaction was carried out for 3 hours to polyoxyethylene (7) distyreneated methylphenyl ether monosulfate ammonium salt (dispersion). Agent C-5) was obtained.
Table 3 shows the chemical structure of the dispersant obtained in the above production example.

[Manufacturing 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, and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75 ° C.) were 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 at 90 to 95 ° C. using an ultrasonic homogenizer "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.) for 20 minutes and then to room temperature (20 ° C.). Cooled. Deionized water was added to adjust the solid content concentration to 20% by mass to obtain a wax particle dispersion liquid D-1. The volume median particle diameter D ₅₀ of the wax particles in the dispersion was 0.47 μm, and the CV value was 27%.

[Manufacturing of colorant particle dispersion (step 3)]
Manufacturing example Z1
(Manufacture of Colorant Particle Dispersion Liquid Z-1)
A beaker with an internal volume of 1 L is mixed with 100 g of magenta pigment "Permanent Carmin 3810" (manufactured by Sanyo Pigment Co., Ltd., CI Pigment Red 269), 35 g of dispersant C-1, and 300 g of deionized water, and a homomixer " After dispersing for 1 hour at a stirring blade rotation speed of 8000 rpm using "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), "Microfluidizer M-110EH" (manufactured by Microfluidics) After 15PASS treatment at a pressure of 150 MPa using the above, a 200-mesh filter was passed through, and deionized water was added so that the solid content concentration became 24% by mass to obtain a colorant particle dispersion liquid Z-1. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles are shown in Table 4.

Production Examples Z2 to Z5
(Manufacture of Colorant Particle Dispersion Liquids Z-2 to Z-5)
A colorant particle dispersion was obtained in the same manner as in Production Example Z1 except that the dispersant to be added was changed as shown in Table 4. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles are shown in Table 4.

Production example Z6
(Manufacturing of Colorant Particle Dispersion Liquid Z-6)
A colorant particle dispersion Z-6 was obtained in the same manner as in Production Example Z1 except that the amount of the dispersant to be added was changed from 35 g to 20 g. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles are shown in Table 4.

Manufacturing example Z7
(Manufacturing of Colorant Particle Dispersion Liquid Z-7)
A colorant particle dispersion Z-7 was obtained in the same manner as in Production Example Z1 except that the colorant was changed to 100 g of a cyan pigment "ECB-301" (copper phthalocyanine pigment manufactured by Dainichiseika Kogyo Co., Ltd.). Volume-median particle size D ₅₀ and CV value of the obtained colorant particles are shown in Table 4.

Production example Z8
(Manufacturing of Colorant Particle Dispersion Liquid Z-8)
A colorant particle dispersion Z-8 was obtained in the same manner as in Production Example Z1 except that the colorant was changed to 100 g of the yellow pigment "Hanza Yellow 5GX01" (manufactured by Clariant Chemicals Co., Ltd., CI Pigment Yellow 74). It was. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles are shown in Table 4.

Manufacturing example Z9
(Manufacturing of Colorant Particle Dispersion Liquid Z-9)
In a beaker with an internal volume of 1 L, 100 g of magenta pigment "Permanent Carmine 3810" (manufactured by Sanyo Pigment Co., Ltd., CI Pigment Red 269), 15 mass% sodium dodecylbenzene sulfonate aqueous solution "Neoperex G-15" (Kao Co., Ltd.) 233 g of anionic surfactant manufactured by the company and 102 g of deionized water are mixed, and a stirring blade is used at room temperature using a homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kika Kogyo Co., Ltd.). After dispersing for 1 hour at a rotation speed of 8000 rpm, 15PASS treatment was performed at a pressure of 150 MPa using "Microfluidizer M-110EH" (manufactured by Microfluidics), and then passed through a 200 mesh filter to bring the solid content concentration to 24% by mass. Deionized water was added so as to obtain a colorant particle dispersion Z-9. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles are shown in Table 4.

Production example Z10
(Manufacturing of Colorant Particle Dispersion Liquid Z-10)
Magenta pigment "Permanent Carmine 3810" (manufactured by Sanyo Pigment Co., Ltd., CI Pigment Red 269) 100 g, polyoxyethylene (13) oleyl ether "Emargen 420" (manufactured by Kao Co., Ltd., nonion) in a beaker with an internal volume of 1 L. 35 g of (sexual surfactant) was dissolved in 300 g of deionized water, and an aqueous active agent solution was added and mixed, and the homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kagaku Kogyo Co., Ltd.) was used at room temperature. After dispersing for 1 hour at a stirring blade rotation speed of 8000 rpm, 15PASS treatment was performed at a pressure of 150 MPa using "Microfluidizer M-110EH" (manufactured by Microfluidics), and then passed through a 200 mesh filter to obtain a solid content concentration of 24. A colorant particle dispersion Z-8 was obtained by adding deionized water so as to have a mass%. Volume-median particle size D ₅₀ and CV value of the obtained colorant particles are shown in Table 4.

[Manufacturing of toner]
Example 1
(Preparation of toner 1)
300 g of resin particle dispersion liquid X-1, 34 g of wax particle dispersion liquid D-1, and colorant particle dispersion liquid Z-1 are placed in a four-necked flask having an internal volume of 3 L equipped with a dehydration tube, a stirrer, and a thermocouple. 30 g and 6 g of a 10% by mass aqueous solution of polyoxyethylene (50) lauryl ether "Emulgen 150" (manufactured by Kao Co., Ltd., nonionic surfactant) were mixed at a temperature of 25 ° C. (above, step 4). Next, while stirring the mixture, a solution prepared by adding a 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution prepared by dissolving 19 g of ammonium sulfate in 179 g of deionized water to adjust the pH to 8.6 was applied at 25 ° C. for 5 minutes. The temperature was raised to 60 ° C. over 2 hours, and the mixture was held at 60 ° C. until the volume median particle diameter D _{50 of} the agglomerated particles reached 5.2 μm to obtain a dispersion of agglomerated particles (above , Step 5).
To the obtained dispersion of agglomerated particles, 10 g of polyoxyethylene lauryl ether sulfate sodium "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. Then, the temperature was raised to 75 ° C. over 1 hour, and then the temperature was maintained at 75 ° C. until the circularity became 0.970 to obtain a dispersion liquid of fused particles in which aggregated particles were fused (the above steps). 6).
The obtained fused particle dispersion was cooled to 30 ° C., the dispersion was suction-filtered to separate solids, washed with deionized water at 25 ° C., and suction-filtered at 25 ° C. for 2 hours. Then, 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 5 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 (registered trademark) TS720" (Cabot Japan Co., Ltd.) Company-made, number average particle size; 0.012 μm) 1.0 part by mass was placed in a Henshell 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 5.

Examples 2-5, 7-12, Comparative Examples 1-4
(Preparation of toners 2-5 and 7-16)
A toner was prepared in the same manner as in Example 1 except that the type of the resin particle dispersion liquid and the type of the colorant particle dispersion liquid used were changed as shown in Table 5. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 6
(Preparation of toner 6)
Toners were prepared in the same manner as in Example 1 except that the colorant particle dispersion used was changed to Z-6 and the amount was changed to 27 g. Table 5 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 was used as the dispersant for the colorant particle dispersion, it reacted with the addition polymer segment, which is an addition polymer of the raw material monomer containing the polyester segment and the styrene compound. It can be seen that a toner showing a high image density of a printed matter can be obtained by using it together with resin particles containing a composite resin having a unit derived from a sex monomer.

Claims (6)

A method for producing a toner for static charge image development, which comprises 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 which is an addition polymerization of a raw material monomer containing a polyester segment and a styrene compound and a unit derived from a bireactive monomer.
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).

[In the formula, R ¹ is an alcoholic group having 1 or more and 12 or less carbon atoms, m indicates the average number of substitutions, m has a value of 1 or more and 4 or less, and R ² is a hydrogen atom or 1 or more and 12 carbon atoms. The following alkyl groups, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of moles of alkylene oxide added, and the value of n is 5 or more and 100 or less. , M is ammonium, tetraalkylammonium, or alkali metal. ] The method for producing a toner for static charge image development according to claim 1, further comprising a step of mixing a dispersion liquid containing resin particles and a dispersion liquid containing colorant particles before the step of aggregating and fusing. .. The method for producing a toner for static charge image development according to claim 1 or 2, wherein the amount of the styrene compound in the addition polymerization resin segment is 50% by mass or more in the raw material monomer. The static charge image developing toner according to any one of claims 1 to 3, wherein in the addition polymerization resin segment, the raw material monomer further contains a vinyl-based monomer having an aliphatic hydrocarbon group having 3 or more and 22 or less carbon atoms. Production method. The method for producing an electrostatic charge image developing toner according to claim 4, wherein the vinyl-based monomer has an aliphatic hydrocarbon group having 8 or more carbon atoms and 22 or less carbon atoms. When the colorant and the compound represented by the formula (1) are mixed, 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. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 5.