JP7042226B2 - Toner manufacturing method - Google Patents

Description

The present invention relates to a method for producing toner used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc., and a toner and the like.

In the field of electrophotographic, with the development of electrophotographic systems, there is a demand for the development of toners for electrophotographics that can achieve 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, a coagulation fusion method (emulsification) in which fine resin particles and the like are aggregated and fused in an aqueous medium to obtain toner. The so-called chemical toner is manufactured by the agglomeration method and the agglomeration union method).

In Patent Document 1, a toner having a step of mixing a dispersion liquid of a colorant-containing polymer particle and a dispersion liquid of resin particles substantially free of a colorant to agglomerate the colorant-containing polymer particles and the resin particles. In the production method of the above, the polymer constituting the colorant-containing polymer particles has (a) a structural unit derived from a salt-forming group-containing monomer and (b) a structural unit derived from an aromatic ring-containing monomer. A method for manufacturing a photographic toner is described. According to the toner, it is described that the dispersibility of the colorant is excellent and the image density can be remarkably improved.
In Patent Document 2, 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 (C). ) Is contained in the shell portion, and the composite resin (A) is obtained by polycondensing an alcohol component containing 80 mol% or more of a propylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component. A composite resin containing a segment (a1) made of a polyester resin and a vinyl-based resin segment (a2) containing a structural unit derived from a styrene-based compound, wherein the crystalline polyester (B) has 8 or more carbon atoms and 16 or less carbon atoms. It is obtained by polycondensing an alcohol component containing 80 mol% or more of α, ω-aliphatic diol and a polyvalent carboxylic acid component containing 80 mol% or more of an aliphatic saturated dicarboxylic acid having 8 or more and 16 or less carbon atoms. It is a crystalline polyester, and the polyester resin (C) is a polyester resin obtained by polycondensing an alcohol component containing 80 mol% or more of an ethylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component. The image development toner is described. According to the toner, it is described that both excellent low-temperature fixing property and heat-resistant storage property are compatible, and the chargeability is also excellent.

Japanese Unexamined Patent Publication No. 2010-26106 Japanese Unexamined Patent Publication No. 2016-114934

Compared to the methods of Patent Documents 1 and 2, there is a demand for a toner that can obtain a higher image density even if the amount of toner used is small. Further, from the viewpoint of the manufacturing method, there is a demand for a manufacturing method in which toner can be obtained in a high yield due to the demand for resource saving.
The present invention relates to a method for producing a toner and a toner for obtaining a toner having a high image density in a high yield.

The present inventors improve the image density by combining the resin particles containing a specific amorphous polyester resin and the crystalline polyester resin with the colorant particles containing a specific addition polymer, and further produce them. It was found that the yield of toner in the above was improved.
The present invention relates to the following [1] and [2].
[1] A method for producing a toner, which comprises a step of aggregating and fusing resin particles and colorant particles in an aqueous medium.
The resin particles contain, in the same or different particles, an amorphous polyester resin which is a polycondensate of an alcohol component containing an aromatic alcohol and a carboxylic acid component, and a crystalline polyester resin.
The colorant particles contain a colorant and an addition polymer of a raw material monomer containing an addition-polymerizable monomer having an aromatic group.
A method for producing a toner, wherein the mass ratio of the colorant to the addition polymer in the colorant particles is 50/50 or more and 95/5 or less.
[2] A toner containing toner particles containing an amorphous polyester resin, a crystalline polyester resin, an addition polymer, and a colorant.
The amorphous polyester resin is a polycondensate of an alcohol component containing an aromatic alcohol and a carboxylic acid component.
The addition polymer is an addition polymer of a raw material monomer containing an addition-polymerizable monomer having an aromatic group.
A toner having a mass ratio of 50/50 or more and 95/5 or less of the colorant and the addition polymer.

According to the present invention, there is provided a method for producing a toner and a toner for obtaining a toner having a high image density in a high yield.

[Toner manufacturing method]
The method for producing a toner of the present invention includes a step of aggregating and fusing resin particles and colorant particles (hereinafter, also referred to as “colorant particles Z”) in an aqueous medium.
The resin particles are crystalline with an amorphous polyester resin (hereinafter, also simply referred to as "resin A") which is a polycondensate of an alcohol component containing an aromatic alcohol and a carboxylic acid component in the same or different particles. It contains a polyester resin (hereinafter, also simply referred to as "resin B").
The colorant particles Z contain a colorant and an addition polymer of a raw material monomer containing an addition-polymerizable monomer having an aromatic group (hereinafter, also simply referred to as “addition polymer E”).
The mass ratio of the colorant to the addition polymer in the colorant particles is 50/50 or more and 95/5 or less.
By the above manufacturing method, a toner capable of obtaining a high image density can be obtained in a high yield.

When the toner particles containing the crystalline polyester resin are produced by the emulsion aggregation method, there is a problem that the yield of the toner is lowered. The reason for this is that the crystalline polyester resin and the colorant particles have a relatively high affinity, so that local aggregation occurs due to the crystalline polyester resin and the colorant particles during aggregation and fusion, and the wall surface of the manufacturing kettle and the colorant particles It was considered that this was because adhesion (coarse particles) to the stirring blades and the like was likely to occur.
The present invention is a method for producing a toner, which comprises a step of aggregating and fusing resin particles and colorant particles containing a crystalline polyester resin in an aqueous medium, in which the colorant and addition polymerization having an aromatic group are included. A dispersion liquid of colorant particles containing the addition polymer E of the raw material monomer containing the sex monomer is used in combination. By including the addition polymer E, the dispersion stability of the colorant particles is improved, and the affinity with the crystalline polyester resin is lowered, so that local aggregation is suppressed, so that the yield of the toner particles is increased. Is presumed to have improved.
Further, in the present invention, the resin particles are a non-crystalline polyester resin which is a polycondensate of an alcohol component containing an aromatic alcohol and a carboxylic acid component in the same or different particles, and a crystalline polyester resin. contains. Dispersion of the colorant in the amorphous polyester resin because the aromatic alcohol-derived moiety in the amorphous polyester resin and the aromatic group moiety of the addition polymer in the colorant particles easily interact with each other. Sex improves. Therefore, it is considered that the image density of the printed matter is improved because the dispersibility of the colorant in the obtained 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 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.
With respect to hydrocarbon groups, the statements in parentheses "(iso or tertiary)" and "(iso)" mean both with and without these prefixes, and without these prefixes. If so, indicate normal.
The "aromatic alcohol" means a compound having an aromatic group and having an alcoholic hydroxyl group instead of a phenolic hydroxyl group.
The "aromatic diol" means a compound having two phenolic hydroxyl groups directly bonded to an aromatic group. Further, the "aromatic polyol" means a compound having a plurality of phenolic hydroxyl groups directly bonded to an aromatic group.
"(Meta) acrylic acid" means at least one selected from acrylic acid and methacrylic acid.
"(Meta) acrylate" means at least one selected from acrylates and methacrylates.
"(Meta) acryloyl group" means at least one selected from acryloyl group and methacryloyl group.
"Styrene-based compound" means unsubstituted or substituted styrene.
The "main chain" means the relatively longest bound chain in the addition polymer.

The method for producing a toner according to an embodiment of the present invention is, for example, a step of aggregating resin particles containing resin A and resin B in the same or different particles and colorant particles Z in an aqueous medium to obtain aggregated particles. (Hereinafter, also referred to as "step 1") and a step of fusing the aggregated particles in an aqueous medium (hereinafter, also referred to as "step 2").
including.
Hereinafter, the present invention will be described by taking the embodiment as an example.

<Step 1>
In step 1, resin particles containing resin A and resin B and colorant particles Z are aggregated in the same or different particles in an aqueous medium to obtain aggregated particles. In step 1, in addition to the resin particles and the colorant particles Z, wax and other additives may be aggregated.
In step 1, the resin particles may be any of resin particles X containing resin A, resin particles Y containing resin B, and resin particles XY containing resin A and resin B in the same particles. It is preferable to use the resin particles X containing A and the resin particles Y containing resin B in combination.

(Resin A)
The resin A is an amorphous polyester resin which is a polycondensate of an alcohol component containing an aromatic alcohol and a carboxylic acid component from the viewpoint of obtaining a toner showing a high image density and a high yield.
Examples of the amorphous polyester resin include polyester resin and modified polyester resin. Examples of the modified polyester resin include a urethane modified product of a polyester resin, an epoxy modified product of a polyester resin, and a composite resin containing a polyester resin segment and a vinyl resin segment. Among these, a composite resin is preferable.
The composite resin is, for example, a polyester resin segment which is a polycondensate of an alcohol component containing an aromatic alcohol and a carboxylic acid component, an addition polymerization resin segment which is an addition polymerization of a raw material monomer containing a styrene compound, and the polyester. It contains a structural unit derived from a bireactive monomer bonded to the resin segment and the addition polymerization resin segment via a covalent bond.
From the viewpoint of further improving the image density, the resin A preferably further contains a structural unit derived from a hydrocarbon wax (W1) having at least one of a carboxy group and a hydroxyl group.
Resin A is preferably amorphous.

Examples of the aromatic alcohol include an alkylene oxide adduct of an aromatic diol and an alkylene oxide adduct of a trivalent or higher aromatic polyol.
The amount of aromatic alcohol is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, still more preferably 100 mol, in the alcohol component. %.
Among these, alkylene oxide adducts of aromatic diols are preferable.
The alkylene oxide adduct of the aromatic diol is preferably an alkylene oxide adduct of bisphenol A, and more preferably the formula (I) :.

（式中、ＯＲ¹及びＲ²Ｏはオキシアルキレン基であり、Ｒ¹及びＲ²はそれぞれ独立にエチレン基又はプロピレン基であり、ｘ及びｙはアルキレンオキシドの平均付加モル数を示し、それぞれ正の数であり、ｘとｙの和の値は、１以上、好ましくは１．５以上であり、１６以下、好ましくは８以下、より好ましくは４以下である）で表されるビスフェノールＡのアルキレンオキシド付加物である。
ビスフェノールＡのアルキレンオキシド付加物としては、例えば、ビスフェノールＡ〔２，２－ビス（４－ヒドロキシフェニル）プロパン〕のプロピレンオキシド付加物、ビスフェノールＡのエチレンオキシド付加物が挙げられる。これらは、１種又は２種以上を用いてもよい。これらの中でも、ビスフェノールＡのプロピレンオキシド付加物が好ましい。
ビスフェノールＡのアルキレンオキシド付加物の量は、アルコール成分中、好ましくは７０モル％以上、より好ましくは９０モル％以上、更に好ましくは９５モル％以上であり、そして、１００モル％以下であり、更に好ましくは１００モル％である。

(In the formula, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are independently ethylene or propylene groups, and x and y indicate the average number of adducts of the alkylene oxide, respectively, which are positive. The value of the sum of x and y is 1 or more, preferably 1.5 or more, 16 or less, preferably 8 or less, and more preferably 4 or less). It is an oxide adduct.
Examples of the alkylene oxide adduct of bisphenol A include a propylene oxide adduct of bisphenol A [2,2-bis (4-hydroxyphenyl) propane] and an ethylene oxide adduct of bisphenol A. These may be used alone or in combination of two or more. Among these, the propylene oxide adduct of bisphenol A is preferable.
The amount of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, further, in the alcohol component. It is preferably 100 mol%.

As the alcohol component, in addition to the aromatic alcohol, for example, a linear or branched aliphatic diol, an alicyclic diol, or a trihydric or higher polyhydric alcohol may be contained.
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 oxides of hydrogenated bisphenol A having 2 or more and 4 or less carbon atoms (average number of added moles of 2 or more and 12). The following) Additives are mentioned.
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
These alcohol components may be used alone or in combination of two or more.

Examples of the carboxylic acid component include a dicarboxylic acid and a trivalent or higher valent carboxylic acid.
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, and terephthalic acid. 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 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 90 mol% or more, in the carboxylic acid component. It is 80 mol% or less, more preferably 75 mol% or less.

The linear or branched aliphatic dicarboxylic acid has preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Examples of the linear or branched aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedic acid, and 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.
The amount of the linear or branched aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 10 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% in the carboxylic acid component. It is as follows.

The trivalent or higher valent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid or an anhydride thereof.
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, still more preferably 8 mol% in the carboxylic acid component. And more, preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less.
As these carboxylic acid components, one kind or two or more kinds may be used.

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

When the resin A is a composite resin, the polyester resin segment is the polyester resin described above from the viewpoint of obtaining a toner showing a high image density and a high yield.
When the resin A is a composite resin, the addition polymerization resin segment is an addition polymerization of a raw material monomer containing a styrene-based compound s from the viewpoint of obtaining a better image density.
Examples of the styrene-based compound s include unsubstituted or substituted styrene. Examples of the substituent substituted with styrene include an alkyl group having 1 or more and 5 or less carbon atoms, a halogen atom, an alkoxy group having 1 or more and 5 or less carbon atoms, a sulfo group or a salt thereof.
Examples of the styrene-based compound s include styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. Among these, styrene is preferable.
The content of the styrene-based compound s in the raw material monomer of the addition polymerization resin segment is preferably 50% by mass or more, more preferably 65% by mass or more, further preferably 70% by mass or more, and 100% by mass or less. It is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.

Examples of the raw material monomer other than the styrene compound s include (meth) acrylic acid esters such as alkyl (meth) acrylate, benzyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate; ethylene, propylene, and butadiene. Olefins; Halovinyls such as vinyl chloride; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as vinyl methyl ether; Vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone Can be mentioned. Among these, (meth) acrylic acid ester is preferable, and (meth) acrylic acid alkyl is more preferable.
The carbon number of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 4 or more, still more preferably 6 or more, still more preferably 10 or more, still more, from the viewpoint of obtaining a better image density. It is preferably 14 or more, more preferably 16 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 20 or less.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, and (meth). ) Acrylic acid (iso) amyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid ( Examples thereof include iso) dodecyl, (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl. Among these, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate are preferable, and 2-ethylhexyl (meth) acrylate and (meth) acrylic acid. Dodecyl and stearyl (meth) acrylate are more preferred, dodecyl (meth) acrylate and stearyl (meth) acrylate are even more preferred, and stearyl methacrylate is even more preferred.

The content of the (meth) acrylic acid ester in the raw material monomer of the addition polymerization resin segment is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or more. It is mass% or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.

The total amount of the styrene-based compound s and the (meth) acrylic acid ester in the raw material monomer of the addition polymerization resin segment is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and more. More preferably, it is 100% by mass.

When the resin A is a composite resin, the composite resin preferably has a structural unit derived from a bireactive monomer bonded to a polyester resin segment and an addition polymerization resin segment via a covalent bond.
The “constituent unit derived from the bireactive monomer” means a unit in which the functional group and the unsaturated bond site of the bireactive monomer have reacted.
Examples of the bireactive monomer include an addition polymerizable monomer having at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule. .. Among these, from the viewpoint of reactivity, an addition-polymerizable monomer having at least one functional group selected from a hydroxyl group and a carboxy group is preferable, and an addition-polymerizable monomer having a carboxy group is more preferable.
Examples of the addition polymerizable monomer having a carboxy group include acrylic acid, methacrylic acid, fumaric acid, and maleic acid. 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 amount of the structural unit derived from the bireactive monomer is preferably 1 mol part or more, more preferably 5 mol part or more, still more preferably 8 mol part or more with respect to 100 mol part of the alcohol component of the polyester resin segment of the composite resin. And preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less.

The resin A may have a constituent component derived from the hydrocarbon wax W1.
The constituent component derived from the hydrocarbon wax W1 is, for example, the hydrocarbon wax W1 covalently bonded to the polyester resin segment by reacting with a hydroxyl group or a carboxy group.
The hydrocarbon wax W1 has at least one of a hydroxyl group and a carboxy group. The hydrocarbon wax W1 may have one or both of a hydroxyl group and a carboxy group, but preferably has a hydroxyl group and a carboxy group from the viewpoint of improving the image density of the printed matter.
The hydrocarbon wax W1 is obtained, for example, by modifying an unmodified hydrocarbon wax by a known method. Examples of the raw material of the hydrocarbon wax W1 include paraffin wax, Fishertroph wax, microcrystalline wax, polyethylene wax, and polypropylene wax. Among these, paraffin wax and Fischer-Tropsch wax are preferable.

Examples of commercially available products of hydrocarbon wax having a hydroxyl group include "Unilin 700", "Unilin 425", and "Unilin 550" (all manufactured by Baker Petrolite).

Examples of the hydrocarbon wax having a carboxy group include acid-modified hydrocarbon wax.
Examples of commercially available products of hydrocarbon wax having a carboxy group include maleic anhydride-modified ethylene-propylene copolymer "High Wax 1105A" (manufactured by Mitsui Chemicals, Inc.).

Examples of commercially available products of hydrocarbon wax having a hydroxyl group and a carboxy group include "Paracol 6420", "Paracol 6470", and "Paracol 6490" (all manufactured by Nippon Seiro Co., Ltd.).

The hydroxyl value of the hydrocarbon wax W1 is preferably 35 mgKOH / g or more, more preferably 50 mgKOH / g or more, still more preferably 70 mgKOH / g or more, and preferably 180 mgKOH / g, from the viewpoint of improving the image density of the printed matter. It is g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less.

The acid value of the hydrocarbon wax W1 is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and preferably 30 mgKOH / g or more, from the viewpoint of improving the image density of the printed matter. It is g or less, more preferably 25 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

The total hydroxyl value and acid value of the hydrocarbon wax W1 is preferably 35 mgKOH / g or more, more preferably 40 mgKOH / g or more, still more preferably 60 mgKOH / g or more, still more preferably, from the viewpoint of improving the image density of the printed matter. Is 80 mgKOH / g or more, more preferably 90 mgKOH / g or more, and preferably 210 mgKOH / g or less, more preferably 175 mgKOH / g or less, still more preferably 140 mgKOH / g or less, still more preferably 120 mgKOH / g or less. Is.

The number average molecular weight of the hydrocarbon wax W1 is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and preferably 2000 or less, more preferably 1700, from the viewpoint of improving the image density of the printed matter. Below, it is more preferably 1500 or less.
The method for measuring the hydroxyl value and acid value of the hydrocarbon wax W1 is as described in Examples. The number average molecular weight of the hydrocarbon wax W1 is measured by a gel permeation chromatography method using chloroform as a solvent and polystyrene as a standard substance.

When the resin A is a composite resin, the preferable range of the content of each component is as follows.
The content of the polyester resin segment in the composite resin is preferably 40% by mass or more, more preferably 45% by mass, based on the total amount of the polyester resin segment, the addition polymerization resin segment, and the structural units derived from the bireactive monomers. As mentioned above, it is more preferably 55% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 75% by mass or less.

The content of the addition polymerization resin segment in the composite resin is preferably 10% by mass or more, more preferably 15% by mass, based on the total amount of the polyester resin segment, the addition polymerization resin segment, and the structural units derived from the bireactive monomers. % Or more, more preferably 25% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 45% by mass or less.

The amount of the structural unit derived from the bireactive monomer in the composite resin is preferably 0.1% by mass or more with respect to the total amount of the structural unit derived from the polyester resin segment, the addition polymerization resin segment, and the bireactive monomer. It is more preferably 0.5% by mass or more, further preferably 0.8% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

The amount of the constituent unit derived from the hydrocarbon wax W1 in the composite resin is preferably 0.1 mass by mass with respect to 100 parts by mass of the total amount of the constituent unit derived from the polyester resin segment, the addition polymerization resin segment, and the bireactive monomer. More than parts, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less.

The total amount of the constituent units derived from the polyester resin segment, the addition polymerization resin segment, the bireactive monomer and the hydrocarbon wax W1 in the composite resin is preferably 80% by mass or more, more preferably 90% by mass or more. It is more preferably 95% by mass or more, and 100% by mass or less, and more preferably 100% by mass.

The above amount is calculated based on the ratio of the amounts of the polyester resin segment, the raw material monomer of the addition polymerization resin segment, the bireactive monomer, the structural unit derived from the hydrocarbon wax W1, and the amount of the radical polymerization initiator, and is used in the polyester resin segment and the like. The amount of dehydration due to polycondensation is excluded. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is included in the addition polymerization resin segment for calculation.

The resin A may be produced, for example, by a method including a step A of performing a polycondensation reaction with an alcohol component and a carboxylic acid component.
When the resin A has a structural unit derived from the hydrocarbon wax W1, in the above-mentioned step A, for example, in the presence of the hydrocarbon wax W1 having at least one of a hydroxyl group and a carboxy group, polycondensation of an alcohol component and a carboxylic acid component is performed. Make a reaction.

In step A, if necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, and titanium diisopropyrate bistriethanol amyneate is used as a total amount of 100 alcohol components and carboxylic acid components. 0.01 part by mass or more and 5 parts by mass or less with respect to parts by mass; a total amount of 100 parts by mass of an alcohol component and a carboxylic acid component of an esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) Polycondensation may be carried out by using 0.001 part by mass or more and 0.5 part by mass or less with respect to the parts.
When a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation reaction, it is preferably 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, if necessary. A radical polymerization inhibitor of 0.5 parts by mass or more may be used. Examples of the radical polymerization inhibitor include 4-tert-butylcatechol.
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.

When the resin A is a composite resin, the composite resin is, for example, a step A in which a polycondensation reaction is carried out by an alcohol component and a carboxylic acid component, and a step in which an addition polymerization reaction is carried out by a raw material monomer and a bireactive monomer of an addition polymerization resin segment. It may be manufactured by a method including B.
The process B may be performed after the process A, the process A may be performed after the process B, or the process A and the process B may be performed at the same time.
In step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, and then step B is carried out, and then the rest of the carboxylic acid component is added to the polymerization system, and the polycondensation reaction of step A and both reactions if necessary. A method of further advancing the reaction with the sex monomer is more preferable.

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). Can be mentioned.
The amount of the polymerization initiator used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer of the addition polymerization resin segment.
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, still more preferably 180 ° C. or lower.

(Physical characteristics of resin A)
The softening point of the resin A is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and preferably 140 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 125 ° C. or lower. Is.
The glass transition temperature of the resin A is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 60 ° C. or higher. It is as follows.

The acid value of the resin A is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, further. It is preferably 30 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the resin A can be appropriately adjusted depending on the type of the raw material monomer and the amount used thereof, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate, and their values. Is determined by the method described in the examples.
When two or more kinds of resin 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-mentioned ranges.

(Resin B)
The resin B is a crystalline polyester resin from the viewpoint of obtaining a toner showing a high image density and a high yield.
Resin B is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
The alcohol component preferably contains α, ω-aliphatic diol.
The number of carbon atoms of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. be.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol Can be mentioned. Among these, 1,4-butanediol or 1,10-decanediol is preferable.

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

The alcohol component may contain other alcohol components different from the α, ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α and ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin and penta. Examples thereof include trihydric or higher alcohols such as erythritol and trimethylol propane. These alcohol components may be used alone or in combination of two or more.

The carboxylic acid component preferably contains an aliphatic dicarboxylic acid.
The aliphatic dicarboxylic acid has preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid, dodecanedioic acid, or tetradecanedioic acid is preferable, and sebacic acid is more preferable. As these carboxylic acid components, one kind or two or more kinds may be used.

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

The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Examples of other carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and polyvalent carboxylic acids having a valence of 3 or more. These carboxylic acid components may be used alone or in combination of two or more.

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

(Physical characteristics of resin B)
The softening point of the resin B is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower. Is.

The melting point of the resin B is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably 95 ° C. or lower.

The acid value of the resin B is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less. ..

The softening point, melting point, and acid value of the resin B 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. Those values are obtained by the method described in Examples described later. When two or more kinds of resin B are used in combination, it is preferable that the softening point, melting point, and acid value obtained as a mixture thereof are within the above-mentioned ranges.

Resin B is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. As the conditions for polycondensation, for example, the conditions shown in the polycondensation in the resin A described above can be applied.

The mass ratio [B / A] of the resin B to the resin A is preferably 1/99 or more, more preferably 5/95 or more, still more preferably 10/90 or more, still more preferably 20/80 or more. Then, it is preferably 50/50 or less, more preferably 40/60 or less, and further preferably 35/65 or less.

In the resin component of the toner, the contents of the resin A and the resin B are preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass or less. , And preferably 100% by mass.

[Resin particles X]
The resin particles X contain the resin A from the viewpoint of improving the image density.

[Manufacturing method of resin particles X]
The dispersion liquid of the resin particles X is obtained by dispersing the resin A in an aqueous medium.
The water-based medium preferably contains water as a main component, and the content of water in the water-based 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, 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 or more and 5 or less carbon atoms; dialkyl ketones having 3 or more and 5 or less total carbon atoms such as acetone and methyl ethyl ketone; and cyclic ethers such as tetrahydrofuran. Examples include soluble organic solvents. Among these, methyl ethyl ketone is preferable.

The dispersion can be carried out by a known method, but it is preferably dispersed by a phase inversion emulsification method. Examples of the phase inversion emulsification method include a method of adding an aqueous medium to an organic solvent solution of a resin or a molten resin to invert phase emulsification.

The organic solvent used for phase inversion emulsification is not particularly limited as long as the resin is dissolved, and examples thereof include methyl ethyl ketone.
It is preferable to add a neutralizing agent to the organic solvent solution. Examples of the neutralizing agent include basic substances. Examples of the basic substance include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The degree of neutralization of the resin contained in the resin particles X is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably. Is 100 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less.
The degree of neutralization of the resin contained in the resin particles can be calculated by the following formula.
Degree of neutralization (mol%) = [{mass of neutralizer added (g) / equivalent of neutralizer} / [{weighted average acid value of resin constituting resin particles X (mgKOH / g) x resin particles X Mass of resin constituting (g)} / (56 × 1000)]] × 100

While stirring the organic solvent solution or the melted resin, an aqueous medium is gradually added to invert the phase.
The temperature of the organic solvent solution when the aqueous medium is added is preferably at least the glass transition temperature of the resin constituting the resin particles X, more preferably 50 ° C. or higher, still more preferably, from the viewpoint of improving the dispersion stability of the resin particles X. Is 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower.

After the phase inversion emulsification, if necessary, the organic solvent may be removed 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, and further preferably substantially 0% by mass in the dispersion liquid.

The volume medium particle size D ₅₀ of the resin particles X in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, and preferably 0.08 μm or more, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Is 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.3 μm or less.
The CV value of the resin particles X in the dispersion is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably, from the viewpoint of obtaining a toner that can obtain a high-quality image. Is less than 30%.
The volume median particle size D ₅₀ and the CV value are determined by the methods described in Examples described later.
Any of the resin particles Y containing the resin B and the resin particles XY containing the resin A and the resin B can be produced according to the above-mentioned method. The preferred ranges of the volume median particle diameters _D50 and the CV values of the resin particles Y and the resin particles XY are the same as those described above.

[Colorant particles Z]
The colorant particles Z contain the colorant and the addition polymer E from the viewpoint of obtaining a toner showing a high image density and a high yield. The colorant particles Z have, for example, the addition polymer E on the surface of the colorant, and preferably the surface of the colorant is coated with the addition polymer E.

(Colorant)
As the colorant, all of the dyes, pigments and the like used as colorants for toner can be used. For example, carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, and Rhodamine-B can be used. Examples include base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, monoazoero, disazoero, and isoindrin yellow. The toner may be either black toner or color toner other than black.
Among these, carbon black is preferable.
Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black. Among these, furnace black is preferable from the viewpoint of coloring power and charge control.
The pH value of carbon black is preferably 5 or more, more preferably 6 or more, still more preferably 6.5 or more, and preferably 9 or less, more preferably 8 or less, from the viewpoint of further improving the image density. More preferably, it is 7.5 or less.
Specifically, the pH value of carbon black can be measured by the following procedure.
(1) Collect 5 g of carbon black and 50 mL of distilled water having a pH of 7 in a container and mix them.
(2) This is boiled for 15 minutes and then cooled to room temperature in 30 minutes.
(3) Immerse the electrode of the pH meter in this supernatant and measure the pH.
Examples of the pH meter include "HM30R" (manufactured by DKK-TOA CORPORATION).

The amount of dibutyl phthalate (DBP) oil absorbed by carbon black is preferably 20 ml / 100 g or more, more preferably 30 ml / 100 g or more, still more preferably 35 ml / 100 g or more, and preferably 35 ml / 100 g or more, from the viewpoint of toner charge distribution. It is 90 ml / 100 g or less, more preferably 75 ml / 100 g or less, still more preferably 50 ml / 100 g or less.
The DBP oil absorption amount of carbon black is measured according to "How to determine the oil oil absorption amount" of ISO4656 (JIS K6217-4: 2008).

The BET specific surface area of carbon black is preferably 50 m ² / g or more, more preferably 60 m ² / g or more, still more preferably 90 m ² / g or more, still more preferably 100 m ² / g or more, from the viewpoint of coloring power. be. From the viewpoint of charge distribution, it is preferably 150 m ² / g or less, more preferably 130 m ² / g or less, and further preferably 115 m ² / g or less.
The BET specific surface area of carbon black is measured according to JIS K 6217-2: 2017.

(Additional Polymer E)
The addition polymer E is an addition polymer of a raw material monomer containing an addition-polymerizable monomer a having an aromatic group (hereinafter, also simply referred to as “monomer a”) from the viewpoint of obtaining a toner showing a high image density and a high yield. Is. The addition polymer E contains a structural unit derived from the addition polymerizable monomer a having an aromatic group in the main chain from the viewpoint of further improving the image density and the yield.
The raw material monomer of the addition polymer E contains, in addition to the addition-polymerizable monomer a having an aromatic group, preferably an addition-polymerizable monomer b having an ionic group (hereinafter, also simply referred to as “monomer b”).
Further, the raw material monomer of the addition polymer E is more preferably an addition-polymerizable monomer c having a polyalkylene oxide group (hereinafter, also simply referred to as “monomer c”) or a macromonomer d (hereinafter, simply referred to as “monomer c”) in addition to the monomer b. It further contains at least one selected from (also referred to simply as "monomer d").

The addition polymer E is preferably a water-insoluble addition polymer from the viewpoint of improving the image density.
Here, "water-insoluble" means a property that the dissolved amount of a sample dried at 105 ° C. for 2 hours is less than 10 g when dissolved in 100 g of ion-exchanged water at 25 ° C. until saturated. .. The amount of dissolution is measured in a state where the ionic group of the addition polymer E is 100% neutralized. For example, in the case of an addition polymer having a carboxy group, the dissolution amount is the dissolution amount when the carboxy group of the addition polymer is 100% neutralized with sodium hydroxide.
The amount of the addition polymer E dissolved in water is preferably 5 g or less, more preferably 1 g or less.

The molecular weight of the addition polymerizable monomer a having an aromatic group is preferably less than 1,000, more preferably 800 or less, still more preferably 500 or less, still more preferably 300 or less, and preferably 80 or more. It is preferably 90 or more, more preferably 100 or more.
The addition polymerizable monomer a having an aromatic group is preferably nonionic.
Examples of the addition polymerizable monomer a having an aromatic group include a styrene compound a-1 and an aromatic group-containing (meth) acrylate a-2.
Examples of the styrene-based compound a-1 include substituted or unsubstituted styrene. Examples of the substituent substituted with styrene include an alkyl group having 1 or more and 5 or less carbon atoms, a halogen atom, an alkoxy group having 1 or more and 5 or less carbon atoms, a sulfo group or a salt thereof.
The molecular weight of the styrene-based compound a-1 is preferably less than 1,000, more preferably 800 or less, still more preferably 500 or less, still more preferably 300 or less, and preferably 80 or more, more preferably 90 or more. , More preferably 100 or more.
Examples of the styrene compound a-1 include styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. .. Among these, styrene is preferable.
The amount of the styrene-based compound a-1 is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more in the raw material monomer of the addition polymer E from the viewpoint of further improving the image density. , More preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 98% by mass or less, more preferably 80% by mass or less, still more preferably. It is 65% by mass or less, more preferably 50% by mass or less.

Examples of the aromatic group-containing (meth) acrylate a-2 include benzyl (meth) acrylate.
The amount of the aromatic group-containing (meth) acrylate a-2 is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 5% by mass or more in the raw material monomer of the addition polymer E from the viewpoint of further improving the image density. Is 10% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.

The amount of the addition polymerizable monomer a having an aromatic group is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 5% by mass or more in the raw material monomer of the addition polymer E from the viewpoint of further improving the image density. 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less. It is more preferably 90% by mass or less, still more preferably 80% by mass or less, still more preferably 65% by mass or less, still more preferably 50% by mass or less.

The ionic group in the monomer b means a group that dissociates ions in water.
Examples of the ionic group include a carboxy group, a sulfo group, a phosphoric acid group, an amino group, or a salt thereof.
The ionic group is preferably an anionic group from the viewpoint of improving the dispersion stability of the colorant particles. As the anionic property, an acidic group or a salt thereof is preferable, a carboxy group, a sulfo group, or a salt thereof is more preferable, and a carboxy group, or a salt thereof is further preferable.
Examples of the addition polymerizable monomer having a carboxy group include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, and 2-methacryloyloxymethylsuccinic acid.
Among these, an addition-polymerizable monomer having an anionic group is preferable, (meth) acrylic acid is more preferable, and methacrylic acid is further preferable.
When the monomer b is contained, the amount of the monomer b is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and preferably 8% by mass or more in the raw material monomer of the addition polymer E. Is 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.

The average number of moles of alkylene oxide added to the polyalkylene oxide group of the monomer c is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 30 or less, more preferably 20 or less, further. It is preferably 10 or less.
The monomer c is preferably nonionic.
Examples of the monomer c include polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; alkoxy polyalkylene glycol (meth) acrylates such as methoxypolyethylene glycol (meth) acrylate; and phenoxy (. Examples thereof include aryloxypolyalkylene glycol (meth) acrylates such as ethylene glycol-propylene glycol copolymerization (meth) acrylates.
When the monomer c is contained, the amount of the monomer c is preferably 3% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 20% by mass or more in the raw material monomer of the addition polymer E. Is 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.

Examples of the monomer d include a styrene-based compound polymer having an addition-polymerizable functional group at one end (hereinafter, also referred to as “styrene-based macromonomer”). Examples of the addition-polymerizable functional group include a vinyl group, an allyl group, and a (meth) acryloyl group. Of these, the (meth) acryloyl group is preferred.
In the monomer d, styrene is preferable as the styrene-based compound.
The number average molecular weight of the monomer d is preferably 1,000 or more and 10,000 or less. The number average molecular weight is measured by a gel permeation chromatography method using chloroform containing 1 mmol / L dodecyldimethylamine as a solvent, using polystyrene as a standard substance.
Commercially available styrene-based macromonomers include, for example, "AS-6", "AS-6S", "AN-6", "AN-6S", "HS-6", and "HS-6S" (above, Toagosei Co., Ltd.) and the like.
When the monomer d is contained, the amount of the monomer d is preferably 3% by mass or more, more preferably 6% by mass or more, still more preferably 10% by mass or more, and preferably 10% by mass or more in the raw material monomer of the addition polymer E. Is 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.

Further, the raw material monomer of the addition polymer E may contain an addition-polymerizable monomer (other monomers) other than the monomers a to d.
Examples of other monomers include alkyl (meth) acrylates having an alkyl group having 1 or more and 22 or less carbon atoms (preferably 6 or more and 18 or less), and aromatic group-containing (meth) acrylates. Examples of the aromatic group-containing (meth) acrylate include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
When other monomers are contained, the amount of the other monomers is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 20% by mass or less in the raw material monomer of the addition polymer E. Is 10% by mass or less, more preferably 5% by mass or less.

The weight average molecular weight of the addition polymer E is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 20,000 or more, still more preferably 40,000 or more, from the viewpoint of further improving the image density. , More preferably 48,000 or more, and preferably 200,000 or less, more preferably 90,000 or less, still more preferably 60,000 or less, still more preferably 53,000 or less. The weight average molecular weight can be measured by the method described in Examples.

The addition polymer E can be produced, for example, by copolymerizing a raw material monomer by a known polymerization method. The polymerization method is preferably a solution polymerization method in which the raw material monomer is heated and polymerized in a solvent together with a polymerization initiator, a polymerization chain transfer agent and the like.
Examples of the polymerization initiator include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile).
The amount of the polymerization initiator added is preferably 0.5 parts by mass or more, and preferably 30 parts by mass or less with respect to 100 parts by mass of the raw material monomer.
Examples of the polymerization chain transfer agent include mercaptans such as 2-mercaptoethanol and 3-mercaptopropionic acid.
The amount of the polymerization chain transfer agent added is preferably 0.01 parts by mass or more, and preferably 10 parts by mass or less with respect to 100 parts by mass of the raw material monomer.
After completion of the polymerization reaction, the produced polymer may be isolated and purified by a known method such as reprecipitation or solvent distillation from the reaction solution.

The mass ratio of the colorant to the addition polymer E (colorant / addition polymer E) in the colorant particles is preferably 50/50 or more from the viewpoint of obtaining a toner showing a high image concentration and a high yield, which is preferable. Is 60/40 or more, more preferably 70/30 or more, still more preferably 75/25 or more, and 95/5 or less, preferably 90/10 or less, more preferably 85/15 or less.

[Method for producing colorant particles Z]
The colorant particles Z are obtained, for example, by mixing a colorant and the addition polymer E.
The method for producing the dispersion liquid of the colorant particles Z is not particularly limited, and it suffices if it can be controlled to obtain the colorant particles having a desired volume medium particle size _D50 by using a known kneader, disperser or the like, but it is preferable. , The colorant and the dispersion liquid of the addition polymer E are mixed by a bead mill or a homogenizer.

The method for producing the colorant particles Z is preferably
Step a: After mixing the addition polymer E and the organic solvent, if necessary, a neutralizing agent is mixed, and then an aqueous medium is further mixed to obtain a dispersion liquid of the addition polymer E, and step b: This is a method comprising a step of dispersing the dispersion obtained in step a and the colorant to obtain a dispersion of colorant particles Z.
When the organic solvent is contained, the colorant and the addition polymer are dissolved in the organic solvent, the addition polymer is easily adsorbed on the colorant, and the dispersibility of the colorant can be further improved.
Further, it is preferable that the step b is a step of dispersing the dispersion liquid obtained in the step a and the colorant by a bead mill or a homogenizer.

In step a, it is preferable to first mix the addition polymer E and the organic solvent.
Examples of the organic solvent used here include alkyl alcohols having 1 or more and 3 or less carbon atoms, dialkyl ketones having 3 or more and 5 or less total carbon atoms, and cyclic ethers. Among these, a dialkyl ketone having a total carbon number of 3 or more and 5 or less is preferable, and a methyl ethyl ketone is more preferable. When the addition polymer E is synthesized by the solution polymerization method, the solvent used in the polymerization may be used as it is.

Examples of the neutralizing agent include basic substances. Examples of the basic substance include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The degree of neutralization of the addition polymer E is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, still more preferably 60 mol% or more, still more preferably 80 mol% or more. And preferably 100 mol% or less, more preferably 98 mol% or less, still more preferably 95 mol% or less.
The degree of neutralization of the addition polymer E can be determined by the following formula.
Degree of neutralization (mol%) = [{Mass of neutralizer added (g) / Equivalent of neutralizer} / {Mass ratio of addition-polymerizable monomer having acidic group constituting addition polymer E x addition polymer Mass (g) of E / Molecular weight of addition-polymerizable monomer having an acidic group}] × 100
Examples of the device used for mixing in the step a include a mixing and stirring device provided with an anchor blade, a disper blade, and the like.
The temperature at the time of mixing is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and preferably 40 ° C. or lower, more preferably 30 ° C. or lower, still more preferably 25 ° C. or lower.
The mixing time is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, and preferably 30 hours or less, more preferably 10 hours or less, still more preferably 5 hours or less, still more. It is preferably 3 hours or less, and even more preferably 1 hour or less.

In step b, the mass ratio [colorant / addition polymer E] of the colorant and the addition polymer E is as described above.

The devices used in step b include, for example, a kneader such as a roll mill and a kneader, a homogenizer such as a microfluidizer (manufactured by Microfluidic) and a starburst (manufactured by Sugino Machine Limited), a paint shaker, and a media type disperser such as a bead mill. Can be mentioned. These devices may be used alone or in combination of two or more. Among these, a bead mill and a homogenizer are preferable from the viewpoint of reducing the particle size of the pigment.
When a homogenizer is used, the treatment pressure is preferably 60 MPa or more, more preferably 100 MPa or more, further preferably 130 MPa or more, and preferably 270 MPa or less, more preferably 200 MPa or less, still more preferably 180 MPa or less.
The number of passes is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, and preferably 30 or less, more preferably 25 or less.

It is preferable to remove the organic solvent from the obtained dispersion of the colorant particles Z.
Further, it is preferable that the dispersion liquid of the colorant particles Z is filtered through a wire mesh or the like to remove coarse particles or the like. Further, from the viewpoint of improving the productivity and storage stability of the dispersion liquid, the addition polymer E of the colorant particles may be crosslinked.
Further, various additives such as an organic solvent, a preservative, and an antifungal agent may be added to the dispersion liquid of the colorant particles Z.

In the dispersion liquid of the colorant particles Z, the colorant 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, still more preferably. It is 30% by mass or less, more preferably 25% by mass or less.
The solid content concentration of the dispersion liquid of the colorant particles Z is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 50% by mass or less. It is 40% by mass or less, more preferably 30% by mass or less.

The volume median particle size D ₅₀ of the colorant particles Z is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.1 μm or more, and preferably 0.1 μm or more, from the viewpoint of improving the image density. Is 0.4 μm or less, more preferably 0.3 μm or less, still more preferably 0.2 μm or less.
The CV value of the colorant particles Z is preferably 10% or more, more preferably 20% or more, and preferably 45% or less, more preferably 40% or less, still more preferably, from the viewpoint of improving the image density. It is 35% or less.
The volume median particle diameter D ₅₀ and the CV value of the colorant particles Z are measured by the method of the example.

The amount of the colorant particles Z is preferably 3 parts by mass or more, more preferably 6 parts by mass or more, and further preferably 10 parts by mass or more with respect to 100 parts by mass of the resin particles from the viewpoint of further improving the image density. And, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less.

〔wax〕
The agglutination of the resin particles and the colorant particles Z may be performed in the presence of wax.
Examples of the wax include hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystallin wax, paraffin wax, Fishertropch wax, and sazole wax, or oxides thereof; carnauba wax, montan wax. Alternatively, ester waxes such as deoxidized waxes and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like can be mentioned. These may be used alone or in combination of two or more.
Among these, hydrocarbon wax and ester wax are preferable, and hydrocarbon wax is more preferable.

The melting point of the wax is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 160 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower.

The amount of wax in the toner is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass. Hereinafter, it is more preferably 20% by mass or less.

(Dispersion of wax particles)
The wax is preferably mixed with the resin particles and the colorant particles Z as a dispersion liquid of the wax particles and aggregated.
The dispersion liquid of the wax particles can be obtained by using a surfactant, but it is preferably obtained by mixing the wax and the resin particles P described later. By preparing the wax particles using the wax and the resin particles P, the wax particles are stabilized by the resin particles P, and the wax can be dispersed in the aqueous medium without using a surfactant. It is considered that the dispersion liquid of the wax particles has a structure in which a large number of resin particles P are adhered to the surface of the wax particles.
The type and amount of wax added are the same as those of the above-mentioned wax.

The resin constituting the resin particles P in which the wax is dispersed is preferably a polyester-based resin, and from the viewpoint of improving the dispersibility of the wax in an aqueous medium, a composite resin D having a polyester resin segment and an addition polymerization resin segment is used. It is more preferable to use it.
The softening point of the composite resin D is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and preferably 140 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower.
The preferred range of other resin properties of the composite resin D, 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 can be obtained, for example, by the above-mentioned phase inversion emulsification method.
The volume median particle size D ₅₀ of the resin particles P is preferably 0.01 μm or more, more preferably 0.03 μm or more, and preferably 0.3 μm or less, more preferably, from the viewpoint of dispersion stability of the wax particles. It is preferably 0.2 μm or less.
The CV value of the resin particles P is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably 35% or less, still more preferably, from the viewpoint of dispersion stability of the wax particles. Is less than 30%.

The wax particle dispersion liquid is, for example, a dispersion liquid of wax and resin particles P and, if necessary, an aqueous medium, at a temperature equal to or higher than the melting point of the wax, a strong shearing force of a homogenizer, a high-pressure disperser, an ultrasonic disperser, or the like. It is obtained by dispersing using a disperser having a disperser.
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, further preferably 90 ° C. or higher, and preferably from the softening point of the resin contained in the resin particles P. The temperature is lower than 10 ° C. and 100 ° C. or lower, more preferably 98 ° C. or lower, still more preferably 95 ° C. or lower.

The amount of the resin particles P is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and preferably 90 parts by mass or less, based on 100 parts by mass of the wax. It is preferably 70 parts by mass or less, more preferably 50 parts by mass or less.

The volume medium particle size D ₅₀ of the wax particles is preferably 0.05 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, and preferably 0.3 μm or more, from the viewpoint of obtaining uniform aggregated particles. It is 1 μm or less, more preferably 0.8 μm or less, still more preferably 0.6 μm or less.
The CV value of the wax particles is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably 35% or less, still more preferably 30% or less.
The method for measuring the volume median particle diameter _D50 and the CV value of the wax particles is as described in the examples.

The aggregation of the resin particles and the colorant particles Z may be performed in the presence of other additives in addition to the wax.
Examples of other additives include charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, antiaging agents, and cleaning property improving agents. ..

[Surfactant]
In step 1, when the dispersion liquid of each particle is mixed to prepare the mixed dispersion liquid, the dispersion stability of arbitrary components such as resin particles, colorant particles Z, and wax particles added as needed is improved. From the viewpoint, it may be carried out in the presence of a surfactant. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers.
When a surfactant is used, the total 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. Parts or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

The above-mentioned dispersion liquid of resin particles, dispersion liquid of colorant particles Z, and arbitrary components are mixed by a conventional method. From the viewpoint of efficient aggregation, it is preferable to add an aggregating agent to the mixed dispersion obtained by the mixing.

[Coagulant]
Examples of the flocculant include a cationic surfactant such as a quaternary salt, an organic flocculant such as polyethyleneimine, and an inorganic flocculant. Examples of the inorganic flocculant include inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate; inorganic ammonium salts such as ammonium sulfate, ammonium chloride and ammonium nitrate; and metal complexes having a valence of 2 or more. ..
From the viewpoint of improving the cohesiveness and obtaining uniform agglomerated particles, an inorganic flocculant having a valence of 1 or more and a valence of 5 or less is preferable, an inorganic metal salt having a valence of 1 or more and a divalent or less, an inorganic ammonium salt is more preferable, and an inorganic ammonium salt is preferable. Further preferred, ammonium sulfate is even more preferred.

Using a flocculant, for example, a flocculant of 5 parts by mass or more and 50 parts by mass or less is added to a mixed dispersion containing resin particles of 0 ° C. or higher and 40 ° C. or lower and colorant particles Z with respect to 100 parts by mass of the total amount of resin. Then, the resin particles and the colorant particles Z are aggregated in an aqueous medium to obtain aggregated particles. Further, from the viewpoint of promoting aggregation, it is preferable to raise the temperature of the dispersion after adding the flocculant.

Aggregation may be stopped when the agglomerated particles have grown to an appropriate particle size as toner particles.
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. These may be used alone or in combination of two or more. The aggregation terminator may be added in an aqueous solution.
The amount of the aggregation terminator added is preferably 1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the resin in the resin particles, from the viewpoint of surely preventing unnecessary aggregation. From the viewpoint of reducing the residue on the toner, it is preferably 60 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less.

The volume median particle size _D50 of the agglomerated particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less. be. The volume median particle size _D50 of the agglomerated particles is determined by the method described in Examples described later.

<Step 2>
In step 2, for example, the agglomerated particles are fused in an aqueous medium.
By fusion, each particle contained in the agglomerated particles is fused to obtain fused particles.
The volume median particle size _D50 of the fused particles obtained by fusion is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less. It is more preferably 6 μm or less.

The circularity of the fused particles obtained by fusion is preferably 0.955 or more, more preferably 0.960 or more, and preferably 0.990 or less, more preferably 0.985 or less, still more preferably 0.95 or less. It is 0.980 or less.
It is preferable that the fusion is completed after reaching the above-mentioned preferable circularity.

<Post-treatment process>
A post-treatment step may be performed after step 2, and toner particles are obtained by isolating the fused particles. Since the fused particles obtained in step 2 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. It is preferable to perform washing multiple times.
Next, it is preferable to perform drying. 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.

[Toner particles]
The volume medium particle size D ₅₀ of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, from the viewpoint of obtaining a high-quality image and further improving the cleaning property of the toner. The thickness is preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.

The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, still more preferably 16% or more from the viewpoint of improving the productivity of the toner, and from the viewpoint of obtaining a high-quality image. It is preferably 35% or less, more preferably 30% or less, still more preferably 26% or less, still more preferably 23% or less.
The volume median particle diameter D ₅₀ and the CV value of the toner particles can be measured by the method described in Examples.

[toner]
The toner contains toner particles. The toner particles contain the above-mentioned resin A, the addition polymer E, and the colorant. The mass ratio of the colorant to the addition polymer E is 50/50 or more and 95/5 or less. The preferable range of the mass ratio of the colorant and the addition polymer E is as described above.

[External agent]
Although the toner particles can be used as they are as the toner, it is preferable to use the toner particles obtained by adding a fluidizing agent or the like as an external agent to the surface of the toner particles.
Examples of the external additive include fine particles of an inorganic material such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Of these, hydrophobic silica is preferred.
When the surface treatment of the toner particles is performed using an external additive, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 2 parts by mass, based on 100 parts by mass of the toner particles. It is 3 parts by mass or more, 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 is used for electrostatic charge image development in electrophotographic printing. The toner can be used, for example, as a one-component developer or mixed with a carrier as a two-component developer.
Further, when the toner of the present invention is used for printing, it is possible to obtain an image having few image defects (white spots) and high concealment. This can be thought of as follows. Probably because the colorant also acts as a nucleating agent for the crystallization of the crystalline polyester resin in the toner particles, the dispersibility of the colorant in the toner is improved, so that many crystal domains of the crystalline polyester resin are formed. , It becomes a state of being finely dispersed in the toner. As a result, the wettability and spreadability of the toner on the print medium becomes good at the time of fixing, so that it is considered that the toner has a higher hiding property.
In the image forming method of the present invention, the hiding rate of an image formed on plain paper with a toner adhesion of 0.40 ± 0.02 mg / cm ² is preferably 93% or more, more preferably 94% or more, still more preferably. It is 95% or more, and preferably 100% or less. The concealment rate of an image formed on plain paper (hereinafter, also referred to as "concealment rate of plain paper") is calculated by printing on plain paper using toner and calculating the whiteout area ratio in the image after fixing. Specifically, it is measured by the method of the example.
The image forming method of the present invention may be achieved by any toner, but by using the toner obtained by the manufacturing method of the present invention or the toner of the present invention, the concealment rate of the above-mentioned plain paper can be obtained. Obtainable.
Further, the image forming method of the present invention is a step of each known image forming method using a toner for static charge image development, that is, a charging step of charging the surface of an image holder (photoreceptor), and a charged image holder. A static charge image forming step of forming a static charge image on the surface of the image holder, a developing step of developing the static charge image formed on the surface of the image holder as a toner image, and recording a toner image formed on the surface of the image holder. It has at least a transfer step of transferring to the surface of the medium and a fixing step of fixing the toner image transferred to the surface of the recording medium. In addition to this, a cleaning step for removing the toner remaining on the surface of the image holder, a toner supply step for supplying the toner removed in the cleaning step to the developing means, and the like may be provided.
Further, the toner of the present invention has a hiding ratio of plain paper preferably 93% or more, more preferably 94% or more, further preferably 95% or more, and preferably 100% or less, more preferably 99.9. % Or less.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Each property value was measured and evaluated by the following method.
In the notation such as "alkylene oxide (X)", the numerical value X in parentheses means the average number of moles of alkylene oxide added.

[Measuring method]
[Acid value and hydroxyl value of resin and wax]
The acid value and hydroxyl value of the resin and wax were 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 Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of the sample into an aluminum pan and cool it to 0 ° C at a temperature lowering rate of 10 ° C / min. did. 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 calorific value. Of the observed endothermic peaks, the temperature of the peak with the largest endothermic area is defined as the maximum endothermic temperature (1), and is determined by (softening point (° C)) / (maximum endothermic 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 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.

[Weight average molecular weight of addition polymer]
A gel permeation chromatography method [GPC apparatus "HLC-8320GPC" (GPC apparatus "HLC-8320GPC") using a solution prepared by dissolving phosphoric acid and lithium bromide in N, N-dimethylformamide at concentrations of 60 mmol / L and 50 mmol / L, respectively, as an eluent. Tosoh Corporation), column "TSKgel SuperAWM-H, TSKgel SuperAW3000, TSKgel guardcolum Super AW-H" (manufactured by Tosoh Corporation), flow velocity: 0.5 mL / min], monodisperse polystyrene with a known molecular weight as a standard substance Kit [PStQuick B (F-550, F-80, F-10, F-1, A-1000), PStQuick C (F-288, F-40, F-4, A-5000, A-500), Made by Tosoh Corporation].

[Melting point of wax]
Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of the 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 endotherm was taken as the melting point.

[Volume medium particle size _D50 and CV value of resin particles, colorant particles, and wax particles]
(1) Measuring device: Laser diffraction type particle size measuring machine "LA-920" (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: A sample dispersion was taken in a measurement cell, distilled water was added, and the volume median particle diameter D ₅₀ and the volume average particle diameter D _v were measured at concentrations at which the absorbance was within an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size _Dv ) × 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.), dry 5 g of the measurement sample at a drying temperature of 150 ° C., measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of water content 0.05%). ), The water content (% by mass) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-moisture (% by mass)

[Volume medium particle size of aggregated particles D ₅₀ ]
The volume median particle size _D50 of the agglomerated 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.

[Circularity of fused particles]
The circularity of the fused particles was measured under the following conditions.
-Measuring device: Flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation)
-Preparation of dispersion: The dispersion of fused particles was prepared by diluting with deionized water so that the solid content concentration was 0.001 to 0.05% by mass.
-Measurement mode: HPF measurement mode

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

[Evaluation methods]
[Image density of printed matter]
First, the following fixing test was performed, and the minimum fixing temperature (1) was set.
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 the 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 image 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 500 g cylindrical weight (contact area: 157 mm ² ) was placed and pressed once 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 attached to each printed matter is measured. , Colorimeter "SpectroEye" (manufactured by GretagMacbeth, light emission conditions; standard light source D50, observation field 2 °, density standard DINNB, absolute white standard), and the fixation rate from each reflected image density according to the following formula. Was calculated.
Retention 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 (1).
Next, using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) on the 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 25 mg / cm ² was output.
The temperature of the fuser was set to the minimum fixing temperature (1) + 10 ° C. obtained in the above fixing test, and the toner was fixed in the A4 vertical 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.

[Concealment rate of plain paper]
First, the following fixing test was performed, and the minimum fixing temperature (2) was set.
Using a commercially available printer "C712dnw" (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 0.40 ± 0.02 mg / cm ² A solid image of 3 cm × 4 cm was output (unfixed image) without fixing on A4 paper.
Next, prepare the same printer with a variable temperature fuser, set the temperature of the fuser to 70 ° C, and fix the toner at a speed of 15 sheets / minute (75 mm / s) in the A4 vertical direction to print printed matter. Obtained.
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 image 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 500 g cylindrical weight (contact area: 157 mm ² ) was placed and pressed once 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 attached to each printed matter is measured. , Colorimeter "SpectroEye" (manufactured by GretagMacbeth, light emission conditions; standard light source D50, observation field 2 °, density standard DINNB, absolute white standard), and the fixation rate from each reflected image density according to the following formula. Was calculated.
Retention 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 (2).
Then, using the same unfixed image as above (a solid image of 3 cm × 4 cm with a toner adhesion amount of 0.40 ± 0.02 mg / cm ² ), the minimum fixing temperature (2) + 10 ° C. obtained in the fixing test was used. The temperature of the fuser was set to the temperature, and the toner was fixed at a speed of 15 sheets / minute (75 mm / s) in the A4 vertical direction to obtain a printed matter.
An image of a printed matter was taken with a microscope "DSX510" (manufactured by Olympus Corporation) at 208 times under the conditions of transmitted light observation, objective lens 50 times, exposure 50 ms, ISO sensitivity 200, and no contrast. After that, binarization is performed with the analysis software attached to the DSX510, and the whiteout area ratio of the solid image is calculated with the optical reference (red), the threshold value 56, and the small particle removal 5 μm ² , and the following formula is used. The hiding rate of plain paper was calculated according to the above.
Concealment rate of plain paper (%) = 100-Whiteout area rate (%)

[Manufacturing of resin]
[Manufacturing of amorphous resin]
Production Example A1 (Production of 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 3253 g of a propylene oxide (2.2) adduct of bisphenol A, 1003 g of terephthalic acid, and di. (2-Ethylhexanoic acid) 25 g of tin (II), 2.5 g of 3,4,5-trihydroxybenzoic acid, and 394 g of hydrocarbon wax W1 "Paracol 6490" (manufactured by Nippon Seiwa Co., Ltd.) are added to create a nitrogen atmosphere. Below, the temperature was raised to 235 ° C. with stirring, and the temperature was maintained at 235 ° C. for 8 hours, then the pressure in the flask was lowered, and the temperature was maintained 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 2139 g of styrene, 535 g of stearyl methacrylate, 107 g of acrylic acid, and 321 g of dibutyl peroxide was added dropwise over 3 hours. 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., 129 g of fumaric acid, 94 g of sebacic acid, 214 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 resin A-1. The physical characteristics are shown in Table 1.

Production Examples A2-A4 (Production of Resins A-2 to A-4)
Resins A-2 to A-4 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 characteristics are shown in Table 1.

Manufacturing Example A5 (Manufacturing of Resin A-5)
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 5632 g of a propylene oxide (2.2) adduct of bisphenol A, 1736 g of terephthalic acid, and di. Add 40 g of (2-ethylhexanoic acid) tin (II) and 4.0 g of 3,4,5-trihydroxybenzoic acid, raise the temperature to 235 ° C with stirring under a nitrogen atmosphere, and heat at 235 ° C for 10 hours. After holding, 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 190 ° C., 325 g of sebacic acid and 371 g of trimellitic acid anhydride were added, the temperature was raised to 210 ° C. at 10 ° C./hr, and then the pressure in the flask was lowered. The reaction was carried out at 10 kPa to a desired softening point to obtain resin A-5. The physical characteristics are shown in Table 1.

Production Example D1 (Production of Resin D-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 bisphenol A propylene oxide (2.2) adduct 4313 g, terephthalic acid 818 g, and succinic acid were added. 727 g of 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 to 235 ° C. After holding at ° C. for 5 hours, the pressure in the flask was reduced and the mixture 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 resin D-1. The physical characteristics are shown in Table 1.

[Manufacturing of crystalline resin]
Production Example B1 (Production of Resin B-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 3416 g of 1,10-decanediol and 4084 g of sebacic acid were added, and 135 g was added while stirring. The temperature was raised to ° C., kept at 135 ° C. for 3 hours, and then raised from 135 ° C. to 200 ° C. over 10 hours. Then, 23 g of di (2-ethylhexanoic acid) tin (II) was added and held at 200 ° C. for 1 hour, then the pressure in the flask was lowered, and the mixture was held under a reduced pressure of 8.3 kPa for 1 hour to obtain a resin. B-1 was obtained. The physical characteristics are shown in Table 2.

Production Example B2 (Production of Resin B-2)
Resin B-2 was obtained in the same manner as in Production Example B1 except that the raw material composition was changed as shown in Table 2. The physical characteristics are shown in Table 2.

Production Example B3 (Production of Resin B-3)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 1,10-decanediol (4500 g), fumaric acid (3000 g), and 4-tert-butylcatechol (5 g) were added. .. The temperature was raised to 145 ° C. with stirring, kept at 145 ° C. for 3 hours, and then raised from 145 ° C. to 200 ° C. over 10 hours. Then, 25 g of di (2-ethylhexanoic acid) tin was added, and the mixture was further held at 200 ° C. for 1 hour, the pressure in the flask was lowered, and the mixture was held at 8.3 kPa for 4 hours to obtain resin B-3. .. The physical characteristics are shown in Table 2.

[Manufacturing of resin particle dispersion]
Production Example X1 (Production of Resin Particle Dispersion Liquid X-1)
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, 300 g of resin A-1, 360 g of methyl ethyl ketone and 59 g of deionized water were placed at 73 ° C. for 2 hours. The resin was dissolved by sprinkling. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so as to have a neutralization degree of 50 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. and stirring at 280 r / min (peripheral speed 88 m / min), 600 g of deionized water was added over 60 minutes for phase inversion emulsification. While continuously maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, 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. Table 3 shows the volume median particle diameter _D50 and the CV value of the obtained resin particles.

Production Examples X2 to X5 (Production of resin particle dispersion liquids X-2 to X-5)
Resin particle dispersion liquids X-2 to X-5 were obtained in the same manner as in Production Example X1 except that the type of resin used was changed as shown in Table 3. Table 3 shows the volume median particle diameter _D50 and the CV value of the obtained resin particles.

Production Example XY1 (Production of Resin Particle Dispersion Liquid XY-1)
210 g of resin A-1, 90 g of resin B-1, 300 g of methyl ethyl ketone and 49 g of deionized water are 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. , The resin was dissolved at 73 ° C. for 2 hours. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so as to have a neutralization degree of 50 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. and stirring at 280 r / min (peripheral speed 88 m / min), 600 g of deionized water was added over 60 minutes 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. After that, 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 XY-1 was obtained. Table 3 shows the volume median particle diameter _D50 and the CV value of the obtained resin particles.

Production Example Y1 (Production of Resin Particle Dispersion Liquid Y-1)
In a container with an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube, 300 g of resin B-1 and a mixed solvent of 300 g of methyl ethyl ketone and 41 g of deionized water were placed at 73 ° C. The resin was dissolved over 2 hours. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so as to have a neutralization degree of 55 mol% with respect to the acid value of the resin B-1, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C. and stirring at 280 r / min (peripheral speed 88 m / min), 600 g of deionized water was added over 60 minutes 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 obtain the resin particles. An aqueous dispersion Y-1 was obtained. The physical characteristics are shown in Table 3.

Production Examples Y2 and Y3 (Production of resin particle dispersions Y-2 and Y-3)
Resin particle dispersions Y-2 and Y-3 were obtained in the same manner as in Production Example Y1 except that the type of resin used was changed as shown in Table 3. Table 3 shows the volume median particle diameter _D50 and the CV value of the obtained resin particles.

Production Example P1 (Production of Resin Particle Dispersion Liquid P-1)
200 g of resin D-1 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. rice field. A 5 mass% sodium hydroxide aqueous 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 D-1, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C. and stirring at 280 r / min (peripheral speed 88 m / min), 700 g of deionized water was added over 50 minutes 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 P-1 was obtained. The volume median particle diameter D ₅₀ of the obtained resin particles was 0.09 μm, and the CV value was 23%.

[Manufacturing of wax particle dispersion]
Production Example W1 (Production of Wax Particle Dispersion Liquid W-1)
120 g of deionized water, 86 g of resin particle dispersion P-1 and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seiwa Co., Ltd., melting point 75 ° C.) were added to a beaker having an internal volume of 1 L, and the temperature was 90 to 95 ° C. The temperature was maintained at the same temperature, and the mixture was melted 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 W-1. The volume median particle size _D50 of the wax particles in the dispersion was 0.47 μm, and the CV value was 27%.

Production Example W2 (Production of Wax Particle Dispersion Liquid W-2)
A wax particle dispersion liquid W-2 was obtained in the same manner as in Production Example W1 except that the wax type used was changed to Fischer-Tropsch wax "FNP-0090" (manufactured by Nippon Seiro Co., Ltd., melting point 90 ° C.). The volume median particle size D ₅₀ of the wax particles in the dispersion was 0.45 μm, and the CV value was 28%.

[Manufacturing of addition polymer]
Production Examples E1 to E3 (Synthesis of Addition Polymers E-1 to E-3)
The raw material monomers of the types and amounts shown in Table 4 were mixed to prepare a monomer mixed solution having a total amount of monomers of 100 g.
Nitrogen was substituted inside a four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a stirrer, and a thermocouple, and 18 g of methyl ethyl ketone, 0.03 g of 2-mercaptoethanol, and 10% by mass of the monomer mixture were added. The temperature was raised to 75 ° C. with stirring. While kept at 75 ° C., the remaining 90% by mass of the monomer mixture, 0.27 g of 2-mercaptoethanol, 42 g of methyl ethyl ketone and 2,2'-azobis (2,4-dimethylvaleronitrile) "V-65" A mixed solution containing 3 g (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise from the dropping funnel over 3 hours. After the addition was maintained at 75 ° C. for 2 hours after the completion of the dropping, a solution prepared by dissolving 3 g of V-65 in 5 g of methyl ethyl ketone was added, and the mixture was further maintained at 75 ° C. for 2 hours and at 80 ° C. for 2 hours. Then, methyl ethyl ketone was distilled off under reduced pressure to obtain addition polymers E-1 to E-3. The weight average molecular weight of the obtained addition polymer is shown in Table 4.

Production Example E4 (Synthesis of Additive Polymer E-4)
The addition polymer E-4 was obtained in the same manner as in Production Example E1 except that all 2-mercaptoethanol was not added. The weight average molecular weight was measured by the above-mentioned method and is shown in Table 4.

Production Example E5 (Synthesis of Addition Polymer E-5)
Production example except that the amount of 2-mercaptoethanol in the reaction vessel was changed from 0.03 g to 0.06 g and the amount of 2-mercaptoethanol in the dropping funnel was changed from 0.27 g to 0.54 g. The addition polymer E-5 was obtained in the same manner as in E1. The weight average molecular weight was measured by the above-mentioned method and is shown in Table 4.

[Manufacturing of colorant particle dispersion]
Production Example Z1 (Production of Colorant Particle Dispersion Liquid Z-1)
Put 75 g of the addition polymer E-1 and 630 g of methyl ethyl ketone in a container with an internal volume of 5 L equipped with a stirrer equipped with a disper blade, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube, and dissolve the resin at 20 ° C. I let you. To the obtained solution, 101 g of a 5 mass% sodium hydroxide aqueous solution (the degree of neutralization of the addition polymer E-1 becomes 91 mol%) was added, and further 955 g of deionized water was added, and 20 with a disper blade. The mixture was stirred at ° C. for 10 minutes. Next, 300 g of carbon black "Regal-330R" (manufactured by Cabot Corporation) was added, and the mixture was stirred with a disper blade at 6400 r / min at 20 ° C. for 2 hours. Then, it passed through a 200-mesh filter and treated with a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics) at a pressure of 150 MPa for 15 passes. While stirring the obtained dispersion, methyl ethyl ketone and some water were removed at 70 ° C. under reduced pressure. After cooling, it was passed through a 200 mesh filter and deionized water was added so that the solid content concentration became 20% by mass to obtain a colorant particle dispersion liquid Z-1. Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z2 (Production of Colorant Particle Dispersion Liquid Z-2)
A colorant particle dispersion Z-2 was obtained in the same manner as in Production Example Z1 except that the colorant used was changed to the yellow pigment "Hanza Yellow 5GX01" (manufactured by Clariant Chemicals Co., Ltd., CI Pigment Yellow 74). .. Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z3 (Production of Colorant Particle Dispersion Liquid Z-3)
A colorant particle dispersion Z-3 was obtained in the same manner as in Production Example Z1 except that the colorant used was changed to carbon black "Regal-T30R" (manufactured by Cabot Corporation). Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z4 (Production of Colorant Particle Dispersion Liquid Z-4)
A colorant particle dispersion Z-4 was obtained in the same manner as in Production Example Z1 except that the colorant used was changed to carbon black "Regal-T40R" (manufactured by Cabot Corporation). Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z5 (Production of Colorant Particle Dispersion Liquid Z-5)
A colorant particle dispersion Z-5 was obtained in the same manner as in Production Example Z1 except that the colorant used was changed to the yellow pigment "Paliotor Yellow D1155" (manufactured by BASF, CI Pigment Yellow 185). .. Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z6 (Production of Colorant Particle Dispersion Liquid Z-6)
Similar to Production Example Z1, 75 g of the addition polymer E-1 was dissolved in 630 g of methyl ethyl ketone, and then 101 g of a 5% by mass sodium hydroxide aqueous solution (additional polymer E-1) was added to the obtained solution as a neutralizing agent. (Neutralization degree becomes 91 mol%), 955 g of deionized water was added, and the mixture was stirred at 20 ° C. for 10 minutes with a disper blade. Next, 300 g of carbon black "Regal-330R" (manufactured by Cabot Corporation) was added, and the mixture was stirred with a disper blade at 6400 r / min at 20 ° C. for 2 hours.
Then, through a 200-mesh filter, using a bead mill "NVM-2" (manufactured by IMEX), using glass beads with a bead diameter of 0.6 mm, feeding at a peripheral speed of 10 m / s at a filling rate of 80% by volume. 5 passes were performed at a liquid rate of 0.6 kg / min. While stirring the obtained dispersion, methyl ethyl ketone and some water were removed at 70 ° C. under reduced pressure. After cooling, deionized water was added through a 200-mesh filter so that the solid content concentration became 20% by mass to obtain a colorant particle dispersion liquid Z-6. Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z7 (Production of Colorant Particle Dispersion Liquid Z-7)
The addition polymer E-1 was changed to 138 g, the methyl ethyl ketone was changed to 825 g, the 5 mass% sodium hydroxide aqueous solution was changed to 185 g (the neutralization degree of the addition polymer E-1 was 91 mol%), and the deionized water was changed to 1198 g. A colorant particle dispersion liquid Z-7 was obtained in the same manner as in Production Example Z1 except for the above. Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z8 (Production of Colorant Particle Dispersion Liquid Z-8)
The addition polymer E-1 was changed to 30 g, the methyl ethyl ketone was changed to 490 g, the 5% by mass sodium hydroxide aqueous solution was changed to 40 g (the degree of neutralization of the addition polymer E-1 was 91 mol%), and the deionized water was changed to 780 g. A colorant particle dispersion liquid Z-8 was obtained in the same manner as in Production Example Z1 except for the above. Table 4 shows the volume median particle diameter _D50 and the CV value of the obtained colorant particles.

Production Examples Z9 to Z12 (Production of colorant particle dispersions Z-9 to Z-12)
Colorant particle dispersions Z-9 to Z-12 were obtained in the same manner as in Production Example Z1 except that the addition polymer E-1 was changed to the dispersant type shown in Table 5. Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z13 (Production of Colorant Particle Dispersion Liquid Z-13)
As an addition polymer, 75 g of the styrene acrylic copolymer "Joncryl690" (manufactured by BASF; weight average molecular weight 16500) was added to a mixed solution of 103 g of a 5 mass% sodium hydroxide aqueous solution and 777 g of deionized water, and the disper blade was added. The mixture was stirred at 90 ° C. for 60 minutes. Then, the mixture was cooled to 20 ° C., 300 g of carbon black "Regal-330R" (manufactured by Cabot Corporation) was added, and the mixture was stirred with a disper blade at 6400 r / min at 20 ° C. for 2 hours.
Then, it was passed through a 200-mesh filter and treated with a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics) at a pressure of 150 MPa for 15 passes. Then, the colorant particle dispersion liquid Z-13 was obtained by passing through a 200 mesh filter and adding deionized water so that the solid content concentration became 20% by mass. Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z14 (Production of Colorant Particle Dispersion Liquid Z-14)
Production Example Z1 except that the addition polymer was changed to 75 g of styrene acrylic copolymer "Joncryl 586" (manufactured by BASF, weight average molecular weight 4600), 100 g of 5% by mass sodium hydroxide aqueous solution, and 779 g of deionized water. Similarly, a colorant particle dispersion liquid Z-14 was obtained. Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

Production Example Z51 (Production of Colorant Particle Dispersion Liquid Z-51)
Carbon black "Regal-330R" (manufactured by Cabot) 100 g, 15 mass% sodium dodecylbenzene sulfonate aqueous solution "Neoperex G-15" (manufactured by Kao Co., Ltd., anionic surfactant) 167 g in a beaker with an internal volume of 1 L. , And 102 g of deionized water were mixed, and using a homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), at 20 ° C., the rotation speed of the stirring blade was 8000 r / min. After time-dispersion, 15 passes were performed at a pressure of 150 MPa using a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics). Then, it passed through a 200-mesh filter and deionized water was added so that the solid content concentration became 20% by mass to obtain a colorant particle dispersion liquid Z-51. Table 5 shows the volume median particle diameters _D50 and CV values of the obtained colorant particles.

[Manufacturing of toner]
Example 1 (Preparation of Toner 1)
In a four-necked flask with an internal volume of 3 L equipped with a dehydration tube, a stirrer and a thermocouple, 350 g of resin particle dispersion liquid X-1, 150 g of resin particle dispersion liquid Y-1, and 56 g of wax particle dispersion liquid W-1. , 28 g of wax particle dispersion W-2, 78 g of colorant particle dispersion Z-1, 10 mass of polyoxyethylene (50) lauryl ether "Emulgen 150" (manufactured by Kao Co., Ltd., nonionic surfactant). 15 g of a% aqueous solution and 17 g of a 15 mass% sodium dodecylbenzene sulfonate aqueous solution “Neoperex G-15” (manufactured by Kao Co., Ltd., anionic surfactant) were mixed at a temperature of 25 ° C. 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 40 g of ammonium sulfate in 568 g of deionized water to adjust the pH to 8.6 was applied at 25 ° C. for 10 minutes. The temperature was raised to 61 ° C. over 2 hours, and the mixture was kept at 61 ° C. until the volume median particle size _D50 of the aggregated particles reached 5.2 μm to obtain a dispersion liquid of the aggregated particles.
In the obtained dispersion of agglomerated particles, 48 g of polyoxyethylene lauryl ether sulfate sodium "Emar E-27C" (manufactured by Kao Co., Ltd., anionic surfactant, effective concentration 27% by mass), 313 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 held at 75 ° C. for 30 minutes, 20 g of a 0.1 mol / L sulfuric acid aqueous solution was added, and the mixture was further held at 75 ° C. for 15 minutes. Then, 20 g of a 0.1 mol / L sulfuric acid aqueous solution was added again, and the mixture was kept at 75 ° C. until the circularity became 0.960 to obtain a dispersion liquid of fused particles in which aggregated particles were fused.
The obtained fused particle dispersion was cooled to 30 ° C., the dispersion was suction-filtered to separate the solid content, 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. The amount of toner particles obtained was 111 g. Since the amount of toner particles calculated in preparation (“binding resin” + “colorant + addition polymer” + “wax + resin used for wax dispersion”) is 132 g, the toner yield is 84%. there were. Table 6 shows the physical characteristics 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-manufactured, 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. Table 6 shows the physical characteristics of the obtained toner and the evaluation results of the toner.

Examples 2 to 6, 9 to 21 and Comparative Examples 1 to 2 (manufacturing of toners 2 to 6, 9 to 21, 51 to 52)
Toners 2 to 6, 9 to 21, 51 to 52 were produced 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 6. .. Table 6 shows the physical characteristics of the obtained toner particles, the toner yield, and the evaluation results of the toner.

Example 7 (Preparation of Toner 7)
Toner 7 was produced in the same manner as in Example 1 except that the type of the colorant particle dispersion liquid to be used was changed to the colorant particle dispersion liquid Z-7 and the addition amount thereof was changed to 92 g. Table 6 shows the physical characteristics of the obtained toner particles, the toner yield, and the evaluation results of the toner.

Example 8 (Preparation of Toner 8)
Toner 8 was produced in the same manner as in Example 1 except that the type of the colorant particle dispersion liquid to be used was changed to the colorant particle dispersion liquid Z-8 and the addition amount thereof was changed to 69 g. Table 6 shows the physical characteristics of the obtained toner particles, the toner yield, and the evaluation results of the toner.

Example 22 (Preparation of Toner 22)
The resin particle dispersion liquid X-1 and the resin particle dispersion liquid Y-1 to be used were changed to the resin particle dispersion liquid XY-1, and the toner 22 was prepared in the same manner as in Example 1 except that the addition amount thereof was changed to 500 g. did. Table 6 shows the physical characteristics of the obtained toner particles, the toner yield, and the evaluation results of the toner.

The concealment rate of plain paper was evaluated for Example 1 and Comparative Example 2. The results are shown in Table 7.

As described above, from the results of Examples and Comparative Examples, it can be seen that according to the present invention, it is possible to obtain a toner capable of obtaining a high image density of a printed matter in a high yield. Further, according to the present invention, it can be seen that an image having an excellent concealment rate of plain paper can be obtained.

Claims (7)

A method for producing a toner, which comprises a step of aggregating and fusing resin particles and colorant particles in an aqueous medium.
The resin particles contain, in the same or different particles, an amorphous polyester resin which is a polycondensate of an alcohol component containing an aromatic alcohol and a carboxylic acid component, and a crystalline polyester resin.
The colorant particles contain a colorant and an addition polymer of a raw material monomer containing an addition-polymerizable monomer having an aromatic group.
The colorant particles
Step a: A step of mixing the addition polymer and an organic solvent and then further mixing an aqueous medium to obtain a dispersion liquid of the addition polymer.
Step b: A step of dispersing the dispersion obtained in step a and the colorant to obtain a dispersion of the colorant particles.
Obtained by methods including
A method for producing a toner, wherein the mass ratio of the colorant to the addition polymer in the colorant particles is 50/50 or more and 95/5 or less. The method for producing a toner according to claim 1, wherein the crystalline polyester resin is a polycondensate of an alcohol component containing α, ω-aliphatic diol and a carboxylic acid component. The method for producing a toner according to claim 1 or 2, wherein the addition polymerizable monomer having an aromatic group has a molecular weight of 80 or more and less than 1,000. The method for producing a toner according to any one of claims 1 to 3, wherein the raw material monomer of the addition polymer further contains an addition-polymerizable monomer having an anionic group. The method for producing a toner according to any one of claims 1 to 4, wherein the raw material monomer of the addition polymer further contains an addition-polymerizable monomer having a polyalkylene oxide group. The method for producing a toner according to any one of claims 1 to 5, wherein the colorant is carbon black. The method for producing toner according to any one of claims 1 to 6, wherein the step b is a step of dispersing the dispersion liquid obtained in the step a and the colorant with a bead mill or a homogenizer.