JP7160256B2 - toner - Google Patents

Description

The present invention relates to a method for producing a toner used for developing latent images formed by electrophotography, electrostatic recording, electrostatic printing, and the like, and the toner.

In the field of electrophotography, along with the development of electrophotographic systems, there is a demand for the development of toners that are compatible with higher image quality and higher speed. As a method of obtaining a toner with a narrow particle size distribution and a small particle size corresponding to high image quality, the aggregation fusion method (emulsification Toner is produced by agglomeration method, aggregation coalescence method). Further, in order to improve the basic properties of toner such as low-temperature fixability and storage stability, giving resins a specific structure has been studied.

Patent Document 1 discloses an aqueous dispersion of a binder resin composition for toner containing a polyester resin and a wax (A), wherein the wax (A) is selected from the group consisting of ester waxes and hydrocarbon waxes. the content of the wax (A) is 3 to 50 parts by mass with respect to 100 parts by mass of the polyester resin, and the polyester resin has a melting point of 60 to 110° C., An aqueous dispersion of a binder resin composition for toner, which contains 1 to 20% by mass of a component derived from a hydrocarbon wax (B) having a hydroxyl group and/or a carboxyl group and having a molecular weight of 400 or more, is disclosed. It is described that this makes it possible to obtain a toner excellent in filming resistance, low temperature fixability and hot offset resistance.
In Patent Document 2, polycondensation of a polyhydric alcohol component and a polyvalent carboxylic acid component is carried out in the presence of a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group, and a constituent component derived from the hydrocarbon wax (W1) is obtained. and a step (1) of obtaining an amorphous resin (A) having a polyester resin segment, and a step of dispersing the obtained amorphous resin (A) in an aqueous medium to obtain an aqueous dispersion of resin particles (X). (2) a step (3) of aggregating the obtained resin particles (X) in the presence of the crystalline polyester (B) in an aqueous medium to obtain aggregated particles, and fusing the obtained aggregated particles; A method for producing a toner for electrostatic charge image development is described which includes the step (4) of applying. It is described that the toner obtained by this is excellent in low-temperature fixability and charging property, and is excellent in image density of printed matter.

JP 2015-210277 A JP 2016-136249 A

The toner production methods described in Patent Documents 1 and 2 contain highly hydrophobic components such as waxes and colorants with good dispersibility in the production of toners by an emulsion aggregation method in which shear force is not particularly applied. It is a method that allows
However, with the methods of Patent Documents 1 and 2, it is difficult to say that a toner that satisfactorily satisfies the two contradictory properties of excellent image density of printed matter and anti-offset property can be obtained.

TECHNICAL FIELD The present invention relates to a method for producing a toner exhibiting excellent image density and hot offset resistance of printed matter, and the toner.

The present inventors focused attention on the constituent components of the toner and conducted studies. As a result, by using a resin with a specific structure and two or more types of wax with a specific melting point relationship, both of the two contradictory properties of excellent image density and hot offset resistance can be achieved. found to be effective for

That is, the present invention relates to the following [1] and [2].
[1] Step 1: Resin particles X containing a constituent component derived from hydrocarbon wax W1 having a hydroxyl group or a carboxyl group and an amorphous resin A having a polyester resin segment are treated in an aqueous medium with wax D1, wax D2, and a step of aggregating in the presence of a coloring agent to obtain aggregated particles;
Step 2: a step of fusing the aggregated particles obtained in the step 1;
A method of manufacturing a toner, comprising:
The melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2, and the temperature T at which the aggregated particles are fused in step 2 is at least a temperature lower than the melting point Tm1 of the wax D1 by 10° C. or higher. A method for producing a toner at a temperature not higher than 10°C.
[2] A component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxyl group, an amorphous resin A having a polyester resin segment, a wax D1, a wax D2, and a coloring agent, wherein the wax D1 has a melting point Tm1 is lower than the melting point Tm2 of said wax D2.

According to the present invention, it is possible to provide a method for producing a toner that exhibits excellent image density and hot offset resistance in printed matter, and the toner.

[Toner manufacturing method]
The method for producing the toner of the present invention comprises:
Step 1: Resin particles X containing a constituent component derived from hydrocarbon wax W1 having a hydroxyl group or a carboxyl group and amorphous resin A having a polyester resin segment are mixed in an aqueous medium with wax D1, wax D2, and a colorant. aggregating in the presence of to obtain aggregated particles;
Step 2: a step of fusing the aggregated particles obtained in step 1;
including.
In the toner manufacturing method, the melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2, and the temperature T for fusing the aggregated particles in step 2 is 10° C. lower than the melting point Tm1 of the wax D1. The temperature is equal to or lower than the temperature higher than the melting point Tm2 of the wax D2 by 10°C.
The production method provides a toner exhibiting excellent image density and hot offset resistance in printed matter. Although the reason is not clear, it is considered as follows.

The toner obtained by the production method of the present invention contains a component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxyl group, an amorphous resin A having a polyester resin segment, and at least two waxes D1 and D2. However, the melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2.
In the production method of the present invention, an amorphous resin A having a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxyl group and a polyester resin segment is used. The resin particles X containing the amorphous resin A are formed so that, in an aqueous medium, the constituent component derived from the hydrocarbon wax W1 exists as a hydrophobic group inside, and the more hydrophilic polyester resin segment exists outside. be.
The resin particles X are aggregated in the presence of at least two types of wax D1 and wax D2, and a colorant, so that the wax D1, wax D2, and colorant are included in the aggregated particles. Then, the aggregated particles are heat-fused at a temperature not lower than 10° C. lower than the melting point Tm1 of the wax D1 and not higher than 10° C. higher than the melting point Tm2 of the wax D2. Further, the colorant is finely dispersed in the fused particles by interacting with the component derived from the hydrocarbon wax W1 in the resin. On the other hand, wax D2, which has a high melting point and is difficult to melt, forms moderately sized domains without being excessively finely dispersed in the fused particles. For this reason, it is believed that the obtained toner not only has excellent image density in printed matter, but also has excellent hot offset resistance because the wax can effectively act upon development.

Definitions of various terms used in this specification are shown below.
Whether a resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (°C)/maximum endothermic peak temperature (°C)) in the measurement method described in the Examples below. A crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins are those having a crystallinity index of less than 0.6 or greater than 1.4. The crystallinity index can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate.
In the specification, the carboxylic acid component of the polyester includes not only the compound, but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of each carboxylic acid (the number of carbon atoms in the alkyl group is 1 or more and 3 or less). included.
In the specification, the term "binder resin" is a general term for resin components contained in the toner including the amorphous resin A and the crystalline resin B.
Each step of the manufacturing method of the present invention will be described below.

[Step 1]
In step 1, resin particles X containing a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxyl group (hereinafter also simply referred to as “hydrocarbon wax W1”) and an amorphous resin A having a polyester resin segment are treated with an aqueous This is a step of aggregating in a medium in the presence of wax D1, wax D2, and a colorant to obtain aggregated particles.
Aggregation is preferably carried out in the presence of the crystalline resin B. The crystalline resin B, the wax D1, the wax D2, and the colorant may be contained in the resin particles X, or may be aggregated using a dispersion of these.

Step 1 may include the following steps 1-1 to 1-3.
Step 1-1: Obtaining Amorphous Resin A Having Constituents Derived from Hydrocarbon Wax W1 Having a Hydroxyl Group or a Carboxy Group and a Polyester Resin Segment Step 1-2: Amorphous Resin Obtained in Step 1-1 Process for obtaining an aqueous dispersion of resin particles X containing A Step 1-3: The resin particles X obtained in step 1-2 are aggregated in an aqueous medium in the presence of wax D1, wax D2, and a colorant. Step 1-1 for Obtaining Aggregated Particles The details of step 1-1 are according to the method shown in the method for producing amorphous resin A described later.
The details of step 1-2 are according to the method shown in the method for producing resin particles X described later.
Each component used in step 1 will be described below.

<Amorphous resin A>
The amorphous resin A has a constituent component derived from the hydrocarbon wax W1 having a hydroxyl group or a carboxyl group and a polyester resin segment, from the viewpoint of obtaining a toner exhibiting image density of printed matter and hot offset resistance. The amorphous resin A is, for example, a resin obtained by polycondensation of an alcohol component and a carboxylic acid component in the presence of a hydrocarbon wax W1 having a hydroxyl group or a carboxy group.
From the viewpoint of further improving the image density and hot offset resistance of the toner printed matter, the amorphous resin A has a constituent component derived from the hydrocarbon wax W1 having a hydroxyl group or a carboxyl group, and a polyester resin segment, and preferably further It has an addition polymerized resin segment.

(Constituents derived from hydrocarbon wax W1)
The constituent component derived from the hydrocarbon wax W1 is, for example, the hydrocarbon wax W1 in which a hydroxyl group or a carboxy group is reacted and covalently bonded to the polyester resin segment.
Hydrocarbon wax W1 has a hydroxyl group or a carboxy group. The hydrocarbon wax W1 may have a hydroxyl group, a carboxyl group, or both. and a carboxy group.
The hydrocarbon wax W1 is obtained, for example, by modifying an unmodified hydrocarbon wax by a known method. Raw materials for the hydrocarbon wax W1 include, for example, paraffin wax, Fischer-Tropsch wax, microcrystalline wax, polyethylene wax, and polypropylene wax. Among these, paraffin wax and Fischer-Tropsch wax are preferred.
Examples of commercially available paraffin waxes and Fischer-Tropsch waxes used as raw materials for hydrocarbon wax W1 include "HNP-11", "HNP-9", "HNP-10", "FT-0070", and "HNP-51." ”, and “FNP-0090” (manufactured by Nippon Seiro Co., Ltd.).

A hydrocarbon wax having a hydroxyl group is obtained, for example, by modifying a hydrocarbon wax such as paraffin wax or Fischer-Tropsch wax by oxidation treatment. Examples of the oxidation treatment method include the methods described in JP-A-62-79267 and JP-A-2010-197979. Specifically, there is a method of liquid-phase oxidizing a hydrocarbon wax with an oxygen-containing gas in the presence of boric acid.
Examples of commercially available hydrocarbon waxes having a hydroxyl group include "Uniline 700", "Uniline 425", and "Uniline 550" (manufactured by Baker Petrolite).

Hydrocarbon waxes having a carboxy group include, for example, acid-modified hydrocarbon waxes.
Acid-modified hydrocarbon waxes are obtained, for example, by introducing carboxyl groups into hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax by acid modification. Examples of acid modification methods include the methods described in JP-A-2006-328388 and JP-A-2007-84787. Specifically, an organic peroxide such as dicumyl peroxide as a reaction initiator and a carboxylic acid compound having an unsaturated bond are added to a melt of a hydrocarbon wax as a raw material and reacted to form a carboxylic acid. groups can be introduced.
Commercially available hydrocarbon waxes having a carboxyl group include, for example, maleic anhydride-modified ethylene-propylene copolymer “Hi-Wax 1105A” (manufactured by Mitsui Chemicals, Inc.).

A hydrocarbon wax having a hydroxyl group and a carboxy group can be obtained, for example, by a method similar to the oxidation treatment of a hydrocarbon wax having a hydroxyl group.
Examples of commercially available hydrocarbon waxes having a hydroxyl group and a carboxyl group include "Paracol 6420", "Paracol 6470", and "Paracol 6490" (manufactured by Nippon Seiro Co., Ltd.).

The hydroxyl value of the hydrocarbon wax W1 is preferably 35 mgKOH/g or more, more preferably 40 mgKOH/g or more, still more preferably 50 mgKOH/g, from the viewpoint of improving the image density of the printed matter and the viewpoint of improving the hot offset resistance. Above, more preferably 70 mgKOH/g or more, still more preferably 90 mgKOH/g or more, and preferably 180 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 120 mgKOH/g or less, still more preferably is 100 mgKOH/g or less.

The acid value of the hydrocarbon wax W1 is preferably 1 mgKOH/g or more, more preferably 3 mgKOH/g or more, still more preferably 5 mgKOH/g, from the viewpoint of improving the image density of the printed matter and the viewpoint of improving the hot offset resistance. Above, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, and preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, still more preferably 20 mgKOH/g or less.

The sum of the hydroxyl value and acid value of the hydrocarbon wax W1 is preferably 40 mgKOH/g or more, more preferably 60 mgKOH/g or more, from the viewpoint of improving the image density of printed matter and the viewpoint of improving hot offset resistance. Preferably 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 It is below.

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. 1500 or less, more preferably 1500 or less.
The methods for measuring the hydroxyl value, acid value and number average molecular weight of the hydrocarbon wax W1 are according to the methods described in Examples.

(polyester resin segment)
The polyester resin segment is, for example, a segment made of a polyester resin that is a polycondensate of an alcohol component and a carboxylic acid component.

（式中、ＯＲ及びＲＯはオキシアルキレン基であり、Ｒ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はアルキレンオキサイ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のアルキレンオキサイド付加物である。
ビスフェノールＡのアルキレンオキサイド付加物としては、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〕のポリオキシプロピレン付加物、ビスフェノールＡのポリオキシエチレン付加物が挙げられる。これらの１種又は２種以上を用いることが好ましい。
ビスフェノールＡのアルキレンオキサイド付加物の含有量は、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８０モル％以上、更に好ましくは９０モル％以上、より更に好ましくは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。 Each component of the polyester resin segment of the amorphous resin A will be described below.
Examples of alcohol components include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and polyhydric alcohols having a valence of 3 or more. Among these, aromatic diols are preferred.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(Wherein, OR and RO are oxyalkylene groups, R is each independently an ethylene group or a propylene group, x and y indicate the average number of added moles of alkylene oxide, each a positive number, and x and The sum of y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less).
The alkylene oxide adducts of bisphenol A include, for example, polyoxypropylene adducts of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] and polyoxyethylene adducts of bisphenol A. It is preferable to use one or more of these.
The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and even more preferably 95 mol% or more in the alcohol component, And it is 100 mol % or less, more preferably 100 mol %.

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

Examples of the carboxylic acid component include dicarboxylic acids and polycarboxylic acids having a valence of 3 or more.
Dicarboxylic acids include, for example, aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferable.
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 95 mol% or less, more preferably It is 90 mol % or less, more preferably 80 mol % or less.

The number of carbon atoms in the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Linear or branched aliphatic dicarboxylic acids include, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, and azelaic acid. , 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 dodecylsuccinic acid, dodecenylsuccinic acid, and octenylsuccinic acid. Among these, fumaric acid and succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms are preferable, and fumaric acid is more preferable.
The amount of linear or branched aliphatic dicarboxylic acid in the carboxylic acid component is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, and preferably 30 mol%. Below, more preferably 20 mol % or less, still more preferably 10 mol % or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, such as trimellitic acid.
When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% in the carboxylic acid component. and preferably 30 mol % or less, more preferably 25 mol % or less, still more preferably 20 mol % or less.
These carboxylic acid components can be used alone or in combination of two or more.

The 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, more preferably is less than or equal to 1.2.

(Addition polymerized resin segment)
From the viewpoint of improving the image density of printed matter, the addition polymerization resin segment is preferably an addition polymer of a raw material monomer containing a styrene compound.

Styrenic compounds include substituted or unsubstituted styrene. Examples of substituents include alkyl groups having 1 to 5 carbon atoms, halogen atoms, alkoxy groups having 1 to 5 carbon atoms, sulfonic acid groups, and salts thereof.
Styrenic compounds include, for example, styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts thereof. Among these, styrene is preferred.
The content of the styrene compound in the raw material vinyl monomer of the addition polymerization resin segment is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass, from the viewpoint of improving the image density of printed matter. More preferably, it is 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 87% by mass or less, and even more preferably 85% by mass or less.

Examples of raw material monomers other than styrene compounds include (meth)acrylic acid esters such as alkyl (meth)acrylate, benzyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate; olefins; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; be done. Among these, (meth)acrylic acid esters are preferred, and alkyl (meth)acrylates are more preferred, from the viewpoint of improving the image density of printed matter and the viewpoint of improving hot offset resistance.
The number of carbon atoms in the alkyl group in the alkyl (meth)acrylate is preferably 1 or more, more preferably 6 or more, and still more preferably 6 or more, from the viewpoint of further improving the image density of the printed matter and further improving the hot offset resistance. It is 10 or more, and preferably 24 or less, more preferably 22 or less, and even more preferably 20 or less.
Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, (iso- or tertiary) butyl (meth)acrylate, (meth)acrylate, ) (iso)amyl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, (meth)acrylic acid ( iso)dodecyl, (iso)palmityl (meth)acrylate, (iso)stearyl (meth)acrylate, and (iso)behenyl (meth)acrylate. Among these, 2-ethylhexyl acrylate and stearyl methacrylate are preferred, and stearyl methacrylate is more preferred.
In addition, "(iso or tertiary)" means normal, iso or tertiary, and "(iso)" means normal or iso.
"(Meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid.

From the viewpoint of improving the image density of printed matter, the raw material monomer for the addition polymerization resin segment preferably consists of styrene or contains styrene and (meth)acrylic acid ester, more preferably styrene and (meth)acrylic acid. It contains an ester, and more preferably contains styrene and an alkyl (meth)acrylate having an alkyl group of 6 to 20 carbon atoms.

The content of the (meth)acrylic acid ester in the raw material vinyl monomer of the addition polymerization resin segment is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably, from the viewpoint of improving the image density of the printed matter. It is 15% by mass or more, more preferably 17% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.
The total content of the styrene compound and (meth)acrylic acid ester in the raw material monomers of the addition polymerization resin segment is preferably 80% by mass or more, more preferably 90% by mass, from the viewpoint of further improving the image density of the printed matter. Above, more preferably 95% by mass or more, 100% by mass or less, and even more preferably 100% by mass.

When the amorphous resin A has an addition polymerization resin segment, the amorphous resin A is preferably a structural unit derived from a bi-reactive monomer that is bonded to the polyester resin segment and the addition polymerization resin segment via a covalent bond. have
A “structural unit derived from a bireactive monomer” means a unit obtained by reacting a functional group and an unsaturated bond site of a bireactive monomer.
The bi-reactive monomers include, for example, addition polymerizable monomers having at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule. . Among these, addition polymerizable monomers having a hydroxyl group or a carboxy group are preferable, and addition polymerizable monomers having a carboxy group are more preferable, from the viewpoint of reactivity.
Examples of bi-reactive monomers include acrylic acid, methacrylic acid, fumaric acid, maleic acid, and the like. Among these, acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred, from the viewpoint of reactivity in both polycondensation reaction and addition polymerization reaction.
The amount of the structural unit derived from the bi-reactive monomer is preferably 1 mol part or more, more preferably 5 mol parts or more, still more preferably 8 mol parts per 100 mol parts of the alcohol component of the polyester resin segment of the amorphous resin A. mol parts or more, and preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less.

In the amorphous resin A, the amount of the component derived from the hydrocarbon wax W1 is preferably 1% by mass or more, more preferably 1% by mass or more, from the viewpoint of further improving the image density of the printed matter and further improving the hot offset resistance. is 2% by mass or more, more preferably 3% by mass or more, and is preferably 15% by mass or less, more preferably 12% by mass or less, and still more preferably 10% by mass or less.

The amount of the polyester resin segment in the amorphous resin A is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of further improving the image density of the printed matter and from the viewpoint of further improving the hot offset resistance. , More preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 99% by mass or less, more preferably It is 98% by mass or less, and when it has an addition polymerization resin segment described later, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

The amount of the addition polymerization resin segment in the amorphous resin A is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more, from the viewpoint of further improving the image density of the printed matter. More preferably 25% by mass or more, still more preferably 35% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

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

The total amount of the structural component derived from the hydrocarbon wax W1, the polyester resin segment, the addition polymerization resin segment, and the structural unit derived from the bi-reactive monomer is preferably 80% by mass or more in the amorphous resin A, and more It is preferably 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, and is 100% by mass or less, preferably 99% by mass or less.

The above amount is calculated based on the ratio of the amounts of the polyester resin segment, the raw material monomer for the addition polymerization resin segment, the bi-reactive monomer, and the radical polymerization initiator, and excludes the amount of dehydration due to polycondensation in the polyester resin segment and the like. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is included in the addition polymerization resin segment and calculated.

(Production of amorphous resin A)
Amorphous resin A is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component in the presence of hydrocarbon wax W1 having a hydroxyl group or a carboxy group.
If necessary, an esterification catalyst such as di(2-ethylhexanoic acid) tin (II), dibutyl tin oxide, titanium diisopropylate bistriethanolamine, etc. is added to the total amount of 100 parts by mass of the alcohol component and the carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less, an esterification cocatalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) for 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component Polycondensation may be carried out using 0.001 parts by mass or more and 0.5 parts by mass or less.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 230° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

When the amorphous resin A has an addition polymerization resin segment, for example, step A of the polycondensation reaction by the alcohol component and the carboxylic acid component and addition polymerization reaction by the raw material monomer of the addition polymerization resin segment and the bi-reactive monomer are performed. You may manufacture by the method containing process B.
Process B may be performed after process A, process A may be performed after process B, or process A and process B may be performed simultaneously.
In step A, part of the carboxylic acid component is subjected to a polycondensation reaction, and then step B is performed. More preferred is a method in which the condensation reaction and, if necessary, the reaction with the bi-reactive monomers are further advanced.

The conditions for the polycondensation reaction are as described above.
Radical polymerization initiators for the addition polymerization reaction include, for example, peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2′-azobis(2,4-dimethylvaleronitrile). are mentioned.
The amount of the radical 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.
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.
In the addition polymerization reaction, preferably 0.001 parts by mass or more and 0.5 parts by mass or less of a radical polymerization inhibitor may be used with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component, if necessary. . Examples of radical polymerization inhibitors include 4-tert-butylcatechol.

(Physical properties of amorphous resin A)
The softening point of the amorphous resin A is preferably 70° C. or higher, more preferably 90° C. or higher, and still more preferably 100° C., from the viewpoint of further improving the image density of the printed matter and further improving the hot offset resistance. Above, more preferably 110° C. or higher, and preferably 140° C. or lower, more preferably 135° C. or lower, still more preferably 130° C. or lower.

The glass transition temperature of the amorphous resin A is preferably 30° C. or higher, more preferably 35° C. or higher, still more preferably 40° C., from the viewpoint of further improving the image density of the printed matter and further improving the hot offset resistance. °C or higher, and preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 65°C or lower.

The acid value of the amorphous resin A is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 16 mgKOH/g or more, from the viewpoint of further improving the image density of the printed matter. It is 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, still more preferably 30 mgKOH/g or less.

The softening point, glass transition temperature, and acid value of the amorphous resin A can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. The value is determined by the method described in Examples.
When two or more amorphous resins A are used in combination, the softening point, glass transition temperature and acid value obtained as a mixture are preferably within the ranges described above.

<Crystalline resin B>
Examples of the crystalline resin B include crystalline polyester resins.
A crystalline polyester is a polycondensate of an alcohol component and a carboxylic acid component.

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

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

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

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

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

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

The 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, more preferably is less than or equal to 1.2.

Crystalline resin B is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
The conditions for the polycondensation reaction are as shown in the method for producing the amorphous resin A described above.

(Physical properties of crystalline resin B)
The softening point of the crystalline resin B is preferably 60° C. or higher, more preferably 70° C. or higher, and even more preferably 80° C. or higher, from the viewpoint of improving the image density of the printed matter. From the viewpoint of improving the offset property, the temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 100° C. or lower.

The melting point of the crystalline resin B is preferably 50° C. or higher, more preferably 60° C. or higher, still more preferably 65° C. or higher, and more preferably 100° C. or lower, more preferably 100° C. or higher, from the viewpoint of improving the image density of the printed matter. is 90° C. or lower, more preferably 80° C. or lower.

The acid value of the crystalline resin B is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, from the viewpoint of improving the dispersion stability of the resin particles Y described later, 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 crystalline resin B can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. , is obtained by the method described in the Examples.
When two or more crystalline resins B are mixed and used, the softening point, melting point, and acid value of the mixture are preferably within the above ranges.

<Wax D1 and Wax D2>
In step 1, two types of waxes, wax D1 and wax D2, are used. The melting point Tm1 of wax D1 is lower than the melting point Tm2 of wax D2.
Examples of wax D1 and wax D2 include hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amides.
Hydrocarbon waxes include, for example, polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sasol wax.
Ester waxes include, for example, carnauba wax, montan wax, deacidified waxes thereof, and fatty acid ester waxes. These can use 1 type(s) or 2 or more types.

The wax D1 is preferably a hydrocarbon wax or an ester wax, more preferably a hydrocarbon wax, and even more preferably a paraffin wax.
The melting point Tm1 of the wax D1 is preferably 60° C. or higher, more preferably 65° C. or higher, still more preferably 70° C. or higher, and more preferably 100° C. or lower, more preferably 100° C. or lower, from the viewpoint of further improving the image density of the printed matter. is 90° C. or less, more preferably 80° C. or less.

As the wax D2, hydrocarbon waxes and ester waxes are preferred, hydrocarbon waxes and carnauba waxes are more preferred, hydrocarbon waxes are more preferred, and Fischer-Tropsch waxes are even more preferred.
The melting point Tm2 of wax D2 is preferably 60° C. or higher, more preferably 70° C. or higher, still more preferably 80° C. or higher, and even more preferably 85° C. or higher, from the viewpoint of further improving hot offset resistance, and It is preferably 110° C. or lower, more preferably 100° C. or lower, and still more preferably 95° C. or lower.
The difference |Tm1−Tm2| between the melting point Tm1 of the wax D1 and the melting point Tm2 of the wax D2 is preferably 5° C. or higher, more preferably 8° C. or higher, from the viewpoint of further improving the image density and hot offset resistance of the printed matter. It is preferably 10° C. or higher, more preferably 15° C. or higher, and preferably 30° C. or lower, more preferably 25° C. or lower, and even more preferably 20° C. or lower.

<Colorant>
Examples of the coloring agent include pigments and dyes, and pigments are preferable from the viewpoint of improving the image density of printed matter.
Pigments include cyan pigments, yellow pigments, magenta pigments, and black pigments. The cyan pigment is preferably a phthalocyanine pigment, more preferably copper phthalocyanine. Preferred yellow pigments are monoazo pigments, isoindoline pigments, and benzimidazolone pigments. The magenta pigment is preferably a quinacridone pigment, a soluble azo pigment such as a BONA lake pigment, or an insoluble azo pigment such as a naphthol AS pigment. The black pigment is preferably carbon black.
Examples of dyes include acridine dyes, azo dyes, benzoquinone dyes, azine dyes, anthraquinone dyes, indigo dyes, phthalocyanine dyes, and aniline black dyes.
A coloring agent can be used individually or in combination of 2 or more types.

<Resin Particle X>
The resin particles X contain at least the amorphous resin A.
The resin particles X may contain a crystalline resin B, a coloring agent, a wax D1 and a wax D2.
The resin particles X are obtained as an aqueous dispersion of the resin particles X by dispersing the amorphous resin A and optionally optional components such as the crystalline resin B and a colorant in an aqueous medium.
Dispersion can be carried out using a known method, but it is preferable to disperse by a phase inversion emulsification method. The phase inversion emulsification method includes, for example, a method in which an aqueous medium is added to an organic solvent solution of a resin or a molten resin to effect phase inversion emulsification.

The organic solvent used for phase inversion emulsification is not particularly limited as long as it dissolves the resin, and examples thereof include methyl ethyl ketone.
It is preferable to add a neutralizing agent such as a basic substance to the organic solvent solution. Basic substances include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The use equivalent (mol%) of the neutralizing agent to the acid groups of the resin is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably 120 mol% or less. , more preferably 100 mol % or less.
The equivalent amount (mol%) of the neutralizing agent to be used can be determined by the following formula. Incidentally, the use equivalent of the neutralizing agent is synonymous with the degree of neutralization when it is 100 mol % or less.
Equivalent amount of neutralizing agent used (mol%) = [{added mass of neutralizing agent (g)/equivalent amount of neutralizing agent}/[{weighted average acid value of resin constituting resin particles X (mgKOH/g) x Mass (g) of resin constituting resin particles X}/(56×1000)]]×100

While stirring the organic solvent solution or molten resin, the aqueous medium is gradually added to cause phase inversion.
From the viewpoint of improving the dispersion stability of the resin particles X, the temperature of the organic solvent solution when adding the aqueous medium is preferably at least the glass transition temperature of the resin constituting the resin particles X, more preferably at least 50° C., even more preferably at least 50° C. is 60° C. or higher, even more preferably 70° C. or higher, and is preferably 85° C. or lower, more preferably 80° C. or lower, and even more preferably 75° C. or lower.
After the phase inversion emulsification, if necessary, the organic solvent may be removed from the resulting dispersion by distillation or the like.

The volume-median particle size (D ₅₀ ) of the resin particles X in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, from the viewpoint of obtaining a toner capable of obtaining high-quality images, and , preferably 0.8 μm or less, more preferably 0.4 μm or less, and still more preferably 0.3 μm or less.
From the viewpoint of improving the productivity of the dispersion liquid of the resin particles X, the coefficient of variation (hereinafter also simply referred to as “CV value”) (%) of the particle size distribution of the resin particles X is preferably 5% or more, more preferably It is 10% or more, more preferably 15% or more, and preferably 50% or less, more preferably 40% or less, and still more preferably 35% or less from the viewpoint of obtaining a toner capable of obtaining high-quality images.
The volume-median particle size (D ₅₀ ) and CV value are determined by the methods described in Examples below.

<Resin Particle Y>
The crystalline resin B may be contained in the resin particles Y different from the resin particles X. In that case, in step 1, resin particles X and resin particles Y are aggregated in an aqueous solvent in the presence of wax D1, wax D2, and a colorant to obtain aggregated particles.
The resin particles Y are obtained, for example, by the same method as the resin particles X described above. The volume median particle size ( _D50 ) and CV value are the same as those exemplified above.

<Wax D1 Particles and Wax D2 Particles>
Wax D1 is preferably added as wax D1 particles. Wax D2 is likewise preferably added as Wax D2 particles. In the following, explanations common to wax D1 and wax D2 are simply referred to as "wax".
The method for producing wax particles includes, for example, a method of dispersing wax and an aqueous medium in the presence of a surfactant or the like at a temperature equal to or higher than the melting point of the wax using a dispersing machine; A method of dispersing the medium with a dispersing machine at a temperature equal to or higher than the melting point of the wax can be used. Among these, the latter method is preferred. By preparing the wax particles using the wax and the resin particles Z, the wax particles are stabilized by the resin particles Z, making it possible to disperse the wax in the aqueous medium without using a surfactant. It is considered that the dispersion of wax particles has a structure in which a large number of resin particles Z are attached to the surfaces of the wax particles.

Dispersers used for dispersing wax include, for example, homogenizers, ultrasonic dispersers, and high-pressure dispersers.
Examples of ultrasonic dispersers include ultrasonic homogenizers. Examples of commercially available products include "US-150T", "US-300T", "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.), "SONIFIER (registered trademark) 4020-400", "SONIFIER (registered trademark) ) 4020-800” (manufactured by Branson).
Commercially available high-pressure dispersers include, for example, a high-pressure wet atomization device “Nanomizer (registered trademark) NM2-L200-D08” (manufactured by Yoshida Kikai Kogyo Co., Ltd.).

The resin constituting the resin particles Z that disperse the wax is preferably a polyester resin, and from the viewpoint of improving the dispersibility of the wax in an aqueous medium, more preferably, a polyester resin segment and an addition polymerization resin segment are used. It is a composite resin with
The polyester resin segment and the addition polymerized resin segment of the composite resin are the same as those exemplified for the amorphous resin A described above.
The softening point of the composite resin is preferably 70° C. or higher, more preferably 80° C. or higher, and preferably 140° C. or lower, more preferably 120° C. or lower, and still more preferably 100° C. or lower.
The other preferred ranges of the resin properties of the composite resin, preferred examples of the raw material monomers constituting the resin, and the like are the same as those shown for the amorphous resin A. A dispersion of the resin particles Z can be obtained, for example, by the above-described phase inversion emulsification method.

The solid content concentration of the wax particle dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of improving toner productivity and improving the dispersion stability of the wax particle dispersion. It is preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.

The volume-median particle size (D ₅₀ ) of the wax particles is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.2 μm or more, from the viewpoint of obtaining uniform aggregated particles and improving the image density of printed matter. It is 0.3 μm or more, and preferably 1 μm or less, more preferably 0.8 μm or less, and even more preferably 0.6 μm or less.

The CV value of the wax particles is preferably 10% or more, more preferably 25% or more, from the viewpoint of improving toner productivity, and is preferably 50% or less, more preferably 50% or more, from the viewpoint of obtaining uniform aggregated particles. It is preferably 45% or less, more preferably 42% or less.
Specifically, the volume-median particle size (D ₅₀ ) and CV value of wax particles are determined by the methods described in Examples.

〔式中、Ｒ¹は炭素数１以上１２以下のアルカンジイル基であり、ｍは平均置換数を示し、ｍの値は１以上４以下であり、Ｒ²は水素原子又はメチル基であり、Ａ¹Ｏはオキシアルキレン基を示し、Ａ¹はエチレン基又はプロピレン基であり、ｎはアルキレンオキサイドの平均付加モル数であり、ｎの値は５以上１００以下である。〕 <Colorant particles>
The colorant is preferably added as colorant particles.
A method for producing colorant particles includes, for example, a method of dispersing a colorant and an aqueous medium in the presence of a surfactant or the like using a disperser. Examples of the disperser include the homogenizer and ultrasonic disperser described above. A preferred embodiment of the aqueous medium is the same as the aqueous medium used for the aqueous dispersion of the resin particles X.
The surfactant is preferably a compound represented by the following formula (1) (hereinafter also simply referred to as "compound 1"). That is, the colorant particles are preferably obtained by mixing a colorant and a compound represented by the following formula (1).

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

R ¹ is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 1 to 2 carbon atoms. A plurality of R ¹ may be the same or different, but are preferably the same.
Examples of R ¹ include a methanediyl group (also referred to as a methylene group), an ethane-1,1-diyl group, and an ethane-1,2-diyl group (the above are collectively referred to as "ethanediyl group" or "ethylene group" also called), propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,1-diyl group, butane-1,2-diyl group, butane -1,3-diyl group, butane-1,4-diyl group and butane-2,3-diyl group. Among these, a methanediyl group and an ethanediyl group are preferred, and an ethanediyl group is more preferred.
The value of m is preferably 2 or more and 3 or less.
R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, still more preferably a hydrogen atom.
A ¹ is preferably an ethylene group, or an ethylene group and a propylene group, more preferably an ethylene group.
The value of n is preferably 6 or more, more preferably 9 or more, still more preferably 11 or more, still more preferably 12 or more, and preferably 50 or less, more preferably 30 or less, still more preferably 20 or less. be.

Examples of compound 1 include polyoxyethylene (styrenated phenyl) ether, polyoxyethylene (distyrenated phenyl) ether, polyoxyethylene (distyrenated methylphenyl) ether, polyoxyethylene (tristyrenated phenyl) ether, poly Oxypropylene (Styrenated Phenyl) Ether, Polyoxypropylene (Distyrenated Phenyl) Ether, Polyoxypropylene (Distyrenated Methylphenyl) Ether, Polyoxypropylene (Tristyrenated Phenyl) Ether, Polyoxyethylene (Benzylphenyl) Ether, Polyoxyethylene (dibenzylphenyl) ether, polyoxyethylene (tribenzylphenyl) ether, polyoxypropylene (benzylphenyl) ether, polyoxypropylene (dibenzylphenyl) ether, polyoxypropylene (tribenzylphenyl) ether include be done.
Among these, polyoxyethylene (distyrenated phenyl) ether is preferable from the viewpoint of improving the image density of printed matter. The average number of added moles of this polyoxyethylene group is preferably within the aforementioned range of n.

Commercially available products of Compound 1 include, for example, polyoxyethylene (distyrenated phenyl) ether “Emulgen A-60” (average addition mole number 13, manufactured by Kao Corporation), polyoxyethylene (distyrenated phenyl) ether “Emulgen A -90” (average number of moles added: 18, manufactured by Kao Corporation) and polyoxyethylene (tribenzylphenyl) ether “Emulgen B-66” (average number of moles added: 15, manufactured by Kao Corporation).

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

For mixing the colorant and compound 1, for example, the colorant, compound 1 and aqueous medium are preferably mixed using a disperser to disperse the colorant. By dispersing the colorant with the compound 1 to obtain colorant particles, the affinity between the colorant and the composite resin A is increased at the time of aggregation and fusion, and the image density of the printed matter can be further improved. .
Dispersers include, for example, homomixers, homogenizers, and ultrasonic dispersers. Commercial products of suitable dispersers include, for example, homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kika Kogyo Co., Ltd.), high pressure homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics), ultra A sonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.) can be mentioned.

The solid content concentration of the colorant particle dispersion is preferably 5% by mass or more, more preferably 10% by mass, from the viewpoint of improving the productivity of the toner and the viewpoint of improving the dispersion stability of the colorant particle dispersion. % or more, more preferably 15 mass % or more, and preferably 50 mass % or less, more preferably 40 mass % or less, still more preferably 30 mass % or less.

The volume-median particle size (D ₅₀ ) of the colorant particles is preferably 0.050 μm or more, more preferably 0.080 μm or more, and still more preferably 0.10 μm or more, from the viewpoint of obtaining a toner capable of obtaining high-quality images. and is preferably 0.50 μm or less, more preferably 0.30 μm or less, still more preferably 0.20 μm or less.

The CV value of the colorant particles is preferably 10% or more, more preferably 25% or more from the viewpoint of improving toner productivity, and preferably 50% or less from the viewpoint of obtaining uniform aggregated particles. More preferably 45% or less, still more preferably 42% or less.
Specifically, the volume-median particle diameter (D ₅₀ ) and CV value of the colorant particles are determined by the methods described in Examples.

<Conditions for Step 1>
Preferably, in step 1, resin particles X are mixed with wax D1 particles, wax D2 particles, and colorant particles in an aqueous medium and aggregated to obtain aggregated particles.
An aqueous dispersion of resin particles X, a dispersion of wax D1 particles, a dispersion of wax D2 particles, a dispersion of colorant particles, and optionally other optional components such as a surfactant are mixed in an aqueous medium. to obtain a mixed dispersion. Then, the particles in the mixed dispersion are aggregated to obtain aggregated particles.

The blending amount of each component in the mixed dispersion in step 1 is as follows.
From the viewpoint of improving the image density of the printed matter, the amount of the resin particles X to be blended is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. From the viewpoint of obtaining aggregated particles having a desired particle size, the content is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

The content of the amorphous resin A in the binder resin is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 95% by mass or less. It is preferably 90% by mass or less, more preferably 80% by mass or less.
The content of the crystalline resin B is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 50% by mass or more, in the binder resin. is 40% by mass or less, more preferably 30% by mass or less.
The total amount of the amorphous resin A and the crystalline resin B is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 98% by mass in the binder resin. % or more and 100 mass % or less.

The amount of wax D1 to be blended is preferably 2 parts by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of improving the image density of printed matter and the viewpoint of improving hot offset resistance. Above, more preferably 6 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

The amount of wax D2 to be blended is preferably 2 parts by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of improving the image density of printed matter and the viewpoint of improving hot offset resistance. Above, more preferably 6 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

The total blending amount of wax D1 and wax D2 is preferably 4 parts by mass or more, more preferably 4 parts by mass or more, with respect to 100 parts by mass of the binder resin, from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. is 10 parts by mass or more, more preferably 12 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.

The mass ratio of wax D1 and wax D2 (wax D1/wax D2) is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.3 or more, from the viewpoint of further improving the image density and hot offset resistance of printed matter. It is preferably 0.5 or more, and preferably 3.5 or less, more preferably 2 or less, and still more preferably 1.5 or less.

From the viewpoint of improving the image density of the printed matter and the viewpoint of improving hot offset resistance, the amount of the colorant compounded is preferably 4 parts by mass or more, more preferably 10 parts by mass, relative to 100 parts by mass of the binder resin. Above, more preferably 12 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

The mixing temperature of each dispersion is preferably 0° C. or higher, more preferably 10° C. or higher, and still more preferably 20° C. or higher, from the viewpoint of controlling aggregation to obtain aggregated particles having a desired particle size. is 40° C. or lower, more preferably 30° C. or lower.

<Flocculant>
From the viewpoint of efficiently aggregating each particle, it is preferable to add an aggregating agent.
Examples of flocculants include cationic surfactants of quaternary ammonium salts, organic flocculants such as polyethyleneimine; inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate; ammonium sulfate, inorganic ammonium salts such as ammonium chloride and ammonium nitrate; and inorganic flocculants such as bivalent or higher metal complexes. From the viewpoint of improving cohesiveness and obtaining uniform aggregated particles, an inorganic flocculant having a valence of 1 to 5 is preferable, an inorganic metal salt having a valence of 1 to 2 and an inorganic ammonium salt are more preferable, and an inorganic ammonium salt is preferable. More preferred, ammonium sulfate is even more preferred.

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

<aggregated particles>
The volume-median particle size ( _D50 ) of the aggregated 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. It is below. The volume-median particle size of the aggregated particles is determined by the method described in Examples below.

After obtaining the aggregated particles, resin particles containing an amorphous resin may be further added to obtain aggregated particles in which the resin particles are adhered to the aggregated particles. Examples of the amorphous resin include amorphous polyester, which is a polycondensate of an alcohol component and a carboxylic acid component exemplified in the amorphous resin A described above. Through this process, toner particles having a core-shell structure are obtained.

In step 1, the aggregation may be stopped when the aggregated particles have grown to a suitable particle size for the toner.
Methods for stopping aggregation include a method of cooling the dispersion, a method of adding an aggregation inhibitor, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation terminator is preferred.

<Aggregation terminator>
Aggregation terminating agents include, for example, surfactants. As the surfactant, an anionic surfactant is more preferable. Anionic surfactants include, for example, alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, and polyoxyalkylene alkyl ether sulfates. An aggregation terminator can be used individually or in combination of 2 or more types. The aggregation terminator may be added as an aqueous solution.
The amount of the aggregation terminator to be added is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the binder resin, from the viewpoint of reliably preventing unnecessary aggregation. , preferably 15 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of reducing the residual amount in the toner.

The temperature at which the aggregation terminator is added is preferably 40° C. or higher, more preferably 45° C. or higher, still more preferably 50° C. or higher, and preferably 80° C. or higher, from the viewpoint of improving toner productivity. It is preferably 70° C. or lower, more preferably 65° C. or lower.

[Step 2]
Step 2 is a step of fusing the aggregated particles obtained in Step 1.
The particles in the aggregated particles, which were mainly in a state of being physically attached to each other, are fused together to form toner particles.

In step 2, the temperature T for fusing the aggregated particles is 10° C. lower than the melting point Tm1 of the wax D1 and 10° C. lower than the melting point Tm2 of the wax D2, from the viewpoint of obtaining a toner exhibiting image density and hot offset resistance in printed matter. It is not higher than a high temperature, and from the viewpoint of further improving the image density of the printed matter, it is preferably at least 5°C lower than the melting point Tm1 of the wax D1, more preferably at least 3°C lower than the melting point Tm1 of the wax D1, still more preferably at least 3°C. is at least 1° C. lower than the melting point Tm1 of wax D1, more preferably at least 1° C. higher than the melting point Tm1 of wax D1, and from the viewpoint of further improving hot offset resistance, preferably the melting point of wax D2. Tm2 or less than 5°C, more preferably 3°C or less than the melting point Tm2 of wax D2, more preferably 3°C or less than wax D2's melting point Tm2, even more preferably 3°C or less than wax D2's melting point Tm2. More preferably, the temperature is 5°C lower than the melting point Tm2 of the wax D2, and even more preferably 10°C lower than the melting point Tm2 of the wax D2.
The temperature T means the temperature around the aggregated particles, for example, the temperature measured by inserting a thermometer into the dispersion to be fused.

In step 2, the temperature T for fusing the aggregated particles is preferably higher than the glass transition temperature of the amorphous resin A from the viewpoint of improving the fusibility of the aggregated particles and improving the productivity of the toner. The temperature is 2°C higher, more preferably 4°C higher, more preferably 6°C higher, and preferably 40°C higher than the glass transition temperature of amorphous resin A, more preferably 40°C higher. The temperature is not higher than 30°C, more preferably not higher than 25°C.

The volume-median particle diameter (D ₅₀ ) of the toner particles in the dispersion liquid obtained by fusion bonding in step 2 is preferably It is 2 µm or more, more preferably 3 µm or more, still more preferably 4 µm or more, and preferably 10 µm or less, more preferably 8 µm or less, and even more preferably 6 µm or less.
The circularity of the toner particles in the dispersion liquid obtained by the fusion in step 2 is preferably 0.955 or more, more preferably 0.960 or more, and still more preferably 0.960 or more, from the viewpoint of further improving the image density of the printed matter. 965 or more, and preferably 0.990 or less, more preferably 0.985 or less, still more preferably 0.980 or less.

[Post-treatment process]
A post-treatment step may be performed after step 2.
The post-treatment step includes, for example, a step of separating the toner particles from the dispersion liquid obtained in step 2.
The toner particles are separated by solid-liquid separation such as suction filtration.
It is preferable that the toner particles are further washed after the solid-liquid separation. From the viewpoint of removing the added surfactant, the toner particles are preferably washed with an aqueous medium at a temperature not higher than the cloud point of the surfactant. Washing is preferably performed multiple times.
It is preferable to dry after washing. Drying methods include, for example, vacuum low temperature drying, vibratory fluidized drying, spray drying, freeze drying, and flash jet.

[toner]
Toner particles are obtained by the above steps.
Although the toner particles can be used as they are as toner, it is preferable to use toner particles in which a fluidizing agent or the like is added to the surface of the toner particles as an external additive, as described later.

The toner contains a component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxyl group, an amorphous resin A having a polyester resin segment, wax D1, wax D2, and a colorant. The content of each component in the toner is the same as the preferred range of the blending amount of each component in step 1 described above.
The toner is, for example, toner for electrostatic charge image development. The electrostatic charge image developing toner is used for developing latent images formed by electrophotography, electrostatic recording, electrostatic printing, and the like.

The volume-median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 2 μm or more, from the viewpoints of improving productivity of toner, improving image density of printed matter, and improving hot offset resistance. is 3 μm or more, more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 6 μm or less.
The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, and still more preferably 16% or more from the viewpoint of improving toner productivity. It is preferably 30% or less, more preferably 26% or less.

Examples of external additives include inorganic fine particles such as hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and carbon black; and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred.
The amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and preferably 10 parts by mass or less with respect to 100 parts by mass of the toner particles. , more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less.

The toner can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

Each property value was measured by the following method. Various evaluations were made by the following methods.

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

[Resin softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature increase rate of 6 ° C./min, a load of 1.96 MPa is applied with a plunger, and the diameter It was extruded through a 1 mm, 1 mm long nozzle. The amount of plunger depression of the flow tester was plotted against the temperature, and the softening point was defined as the temperature at which half of the sample flowed out.
(2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan, and the temperature was lowered from room temperature (20 ° C.) at a rate of 10 ° C./ Cooled to 0° C. at min. Next, the sample was allowed to stand still for 1 minute, then heated to 180°C at a heating rate of 10°C/min, and the calorific value was measured. Among the observed endothermic peaks, the temperature of the peak with the maximum peak area is defined as the maximum endothermic peak temperature (1), and (softening point (°C))/(maximum endothermic peak temperature (1) (°C)) A crystallinity index was determined.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature It was cooled to 0°C at a cooling rate of 10°C/min. Then, the temperature of the sample was increased at a temperature increase rate of 10° C./min, and the calorie was measured. Among the observed endothermic peaks, the temperature of the peak with the maximum peak area was defined as the maximum endothermic peak temperature (2). In the case of crystalline resins, the peak temperature was taken as the melting point.
In the case of an amorphous resin, when a peak is observed, the temperature of the peak is measured. The temperature at the intersection with the extended line of the base line on the low temperature side was taken as the glass transition temperature.

[Melting point of wax]
Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed in an aluminum pan, heated to 200 ° C., and then cooled from 200 ° C. at a cooling rate of 10 ° C./min. was cooled to 0°C. Next, the temperature of the sample was increased at a temperature increase rate of 10° C./min, the calorie was measured, and the maximum endothermic peak temperature was defined as the melting point.

[Number average molecular weight (Mn) of wax]
The number average molecular weight (Mn) was determined by the Gel Permeation Chromatography (GPC) method described below.
(1) Preparation of sample solution A sample was dissolved in chloroform at 25°C to a concentration of 0.5 g/100 mL, and then this solution was filtered through a fluororesin filter with a pore size of 0.2 µm "DISMIC, 25JP" (ADVANTEC Co., Ltd.). (manufactured) to remove undissolved components and obtain a sample solution.
(2) Measurement Using the following measurement apparatus and analysis column, chloroform was flowed as an eluent at a flow rate of 1 mL/min, the column was stabilized in a constant temperature bath at 40°C, and 100 µL of the sample solution was injected. Molecular weight was determined. The molecular weights (weight average molecular weight Mw, number average molecular weight Mn) of the samples were determined by the type names (Mw) of several types of monodisperse polystyrene "TSKgel standard polystyrene": "A-500 (5.0 × 10 ² )", "A- 1000 (1.01×10 ³ )”, “A-2500 (2.63×10 ³ )”, “A-5000 (5.97×10 ³ )”, “F-1 (1.02×10 ⁴ )”, “F-2 (1.81×10 ⁴ )”, “F-4 (3.97×10 ⁴ )”, “F-10 (9.64×10 ⁴ )”, “F-20 ( 1.90×10 ⁵ )”, “F-40 (4.27×10 ⁵ )”, “F-80 (7.06×10 ⁵ )”, “F-128 (1.09×10 ⁶ )” (manufactured by Tosoh Corporation) as a standard sample, it was calculated based on a calibration curve prepared in advance.
・ Measuring device: “HLC-8220GPC” (manufactured by Tosoh Corporation)
・ Analysis column: "GMHXL" and "G3000HXL" (manufactured by Tosoh Corporation)

[Volume Median Particle Diameter (D ₅₀ ) and CV Value of Resin Particles, Colorant Particles, and Wax Particles]
(1) Measuring device: Laser diffraction particle size measuring machine “LA-920” (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size ( _D50 ) and the volume-average particle size were measured at a concentration at which the absorbance was within the appropriate range. Also, the CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution/volume average particle size) x 100

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

[Volume-median particle diameter (D ₅₀ ) of aggregated particles]
(1) Measuring device: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter, Inc.)
(2) Analysis software: "Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter, Inc.)
(3) Measurement conditions:
・Electrolyte solution: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
・Aperture diameter: 50 μm
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. The average particle size ( _D50 ) was determined.

[Volume Median Particle Diameter ( _D50 ) and CV Value of Toner Particles]
The same measurement device, analysis software, aperture diameter, and electrolytic solution as used for the volume median particle diameter (D ₅₀ ) of aggregated particles were used.
(1) Sample dispersion polyoxyethylene lauryl ether “Emulgen (registered trademark) 109P” (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) was dissolved in the electrolytic solution, and the concentration was 5% by mass. A dispersion was obtained.
To 5 mL of the dispersion liquid, 10 mg of a measurement sample of the dried toner particles was added and dispersed for 1 minute with an ultrasonic disperser. to prepare a sample dispersion.
(2) 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. A volume-median particle size ( _D50 ) and a volume-average particle size were obtained from the particle size distribution.
Also, the CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution/volume average particle size) x 100

[evaluation]
[Evaluation of High Temperature Fixability (Hot Offset Resistance) of Toner]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.30 ± 0 A solid image of 0.01 mg/cm ² was output on A4 paper with a length of 50 mm, leaving a margin of 5 mm from the top edge, without being fixed.
Next, the same printer with a variable temperature fixing device was prepared, the temperature of the fixing device was set to 130° C., and the toner was fixed at a speed of 1.5 seconds per sheet of A4 paper in the vertical direction to obtain printed matter. It was visually confirmed that cold offset and hot offset did not occur when the temperature of the fixing device was 130°C.
In the same manner, the temperature of the fixing device was raised from 130° C. by 5° C. to fix the toner to obtain a printed matter, and the occurrence of hot offset was visually confirmed. This test was performed up to the temperature at which hot offset occurred.
Cold offset refers to a phenomenon in which the toner adheres to the fixing roller when the fixing temperature is low because the toner on the unfixed image is not sufficiently melted or the releasability is not good. On the other hand, hot offset means that the viscoelasticity of the toner on the unfixed image is reduced when the fixing temperature is raised to a high temperature, or the releasability is not good at high temperature, so the toner adheres to the fixing roller. refers to phenomena. The occurrence of cold offset or hot offset can be determined by whether or not the toner adheres to the paper again when the fixing roller completes one rotation. I decided no.
The hot offset occurrence temperature refers to the temperature at which hot offset begins to occur. Here, a temperature that is 5° C. lower than the hot offset generation temperature and the maximum temperature at which hot offset does not occur is defined as the hot offset generation temperature.
In the evaluation of the hot offset generation temperature, a difference of 5° C. in the evaluation temperature clearly indicates a difference in toner fixability.

[Image density of printed matter]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.30 mg / cm A solid image of ² was output.
Next, the temperature of the fixing device was set to 130° C., and the toner was fixed at a rate of 1.5 seconds per A4 sheet in the longitudinal direction to obtain a printed matter.
Thirty sheets of high-quality paper "Excellent White Paper A4" (manufactured by Oki Data Co., Ltd.) are placed under the printed matter, and the reflected image density of the solid image portion of the output printed matter is measured with a colorimeter "SpectroEye" (manufactured by GretagMacbeth). Measurement was performed using the irradiation conditions: standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard), and the values obtained by measuring arbitrary 10 points on the image were averaged to obtain the image density. The higher the numerical value, the better the image density.

[Production of resin]
Production Example A1 (Production of Amorphous Resin A-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3268 g of a polyoxypropylene (2.2) adduct of bisphenol A, 1085 g of terephthalic acid, 30 g of di(2-ethylhexanoic acid) tin (II), 3 g of 3,4,5-trihydroxybenzoic acid, and 394 g of hydrocarbon wax W1 "Paracol 6490" (manufactured by Nippon Seiro Co., Ltd.) were added, and a nitrogen atmosphere was added. Then, the temperature was raised to 235° C. while stirring, and after holding at 235° C. for 8 hours, the pressure in the flask was lowered and the pressure was held at 8 kPa for 1 hour. After returning to atmospheric pressure, the system was cooled to 155°C, and a mixture of 2138 g of styrene, 534 g of stearyl methacrylate, 108 g of acrylic acid, and 321 g of dibutyl peroxide was added dropwise over 3 hours while maintaining the temperature at 155°C. Then, after holding at 155° C. for 30 minutes, the temperature was raised to 200° C., the pressure in the flask was further lowered, and the pressure was held at 8 kPa for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 190°C, 70 g of fumaric acid, 269 g of trimellitic anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was raised to 210°C at a rate of 10°C/hr. After that, the reaction was carried out at 8 kPa to the desired softening point to obtain an amorphous resin A-1. Physical properties are shown in Table 1.

Production Examples A2, A4 to A6 (production of amorphous resins A-2, A-4 to A-6)
Amorphous resins A-2, A-4 to A-6 were obtained in the same manner as in Production Example A1, except that the raw material composition was changed as shown in Table 1. Physical properties are shown in Table 1.

Production Example A3 (Production of Amorphous Resin A-3)
The inside of a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4771 g of a polyoxypropylene (2.2) adduct of bisphenol A, 1923 g of terephthalic acid, 30 g of di(2-ethylhexanoic acid) tin (II), 3 g of 3,4,5-trihydroxybenzoic acid, and 349 g of hydrocarbon wax W1 "Paracol 6490" (manufactured by Nippon Seiro Co., Ltd.) were added and placed in a nitrogen atmosphere. With stirring, the temperature was raised to 230°C, maintained at 230°C for 8 hours, then cooled to 180°C, 73 g of dodecenylsuccinic anhydride and 314 g of trimellitic anhydride were added, and the temperature was increased to 220°C at 10°C/hr. After the temperature was raised, the pressure in the flask was lowered, and the reaction was carried out at 8 kPa until the softening point was reached to obtain an amorphous resin A-3. Physical properties are shown in Table 1.

Production Example A7 (Production of Amorphous Resin A-7)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3290 g of a polyoxypropylene (2.2) adduct of bisphenol A, 1092 g of terephthalic acid, Add 30 g of di(2-ethylhexanoic acid) tin (II) and 3 g of 3,4,5-trihydroxybenzoic acid, raise the temperature to 235° C. under a nitrogen atmosphere while stirring, and hold at 235° C. for 8 hours. After that, the pressure in the flask was lowered and maintained at 8 kPa for 1 hour. After returning to atmospheric pressure, the system was cooled to 155°C, and a mixture of 2152 g of styrene, 538 g of stearyl methacrylate, 108 g of acrylic acid, and 323 g of dibutyl peroxide was added dropwise over 3 hours while the temperature was maintained at 155°C. Then, after holding at 155° C. for 30 minutes, the temperature was raised to 200° C., the pressure in the flask was further lowered, and the pressure was held at 8 kPa for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 190°C, 71 g of fumaric acid, 271 g of trimellitic anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was raised to 210°C at a rate of 10°C/hr. After that, the pressure in the flask was lowered, and the reaction was carried out at 4 kPa to the desired softening point to obtain an amorphous resin A-7. Physical properties are shown in Table 1.

Production Example A8 (production of amorphous resin A-8)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4313 g of a polyoxypropylene (2.2) adduct of bisphenol A, 818 g of terephthalic acid, 727 g of succinic acid, 30 g of di(2-ethylhexanoic acid) tin (II), and 3.0 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235°C under a nitrogen atmosphere while stirring. After maintaining the temperature at 235° C. for 5 hours, the pressure in the flask was lowered and the pressure was maintained at 8 kPa for 1 hour. After returning to atmospheric pressure, the system was cooled to 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 while maintaining the temperature at 160°C. Thereafter, the temperature was maintained 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 until the desired softening point was reached to obtain an amorphous resin A-8. Physical properties are shown in Table 1.

Production Example B1 (Production of Crystalline Resin B-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, 3416 g of 1,10-decanediol and 4084 g of sebacic acid were added, and the mixture was stirred while stirring. C. and held at 135.degree. C. for 3 hours, then heated from 135.degree. C. to 200.degree. C. over 10 hours. Then, 23 g of tin (II) di(2-ethylhexanoate) was added, and the temperature was further maintained at 200° C. for 1 hour, the pressure in the flask was reduced, and the temperature was maintained under a reduced pressure of 8 kPa for 1 hour to obtain a crystalline resin. B-1 was obtained. Physical properties are shown in Table 2.

[Production of resin particle dispersion]
Production Example X1 (Production of Resin Particle Dispersion X-1)
210 g of amorphous resin A-1, 90 g of crystalline resin B-1, and 300 g of methyl ethyl ketone were desorbed into a vessel with an internal volume of 3 L equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube. 49 g of ionized water was added, and the resin was dissolved at 73° C. over 2 hours. A 5% by mass sodium hydroxide aqueous solution was added to the resulting solution so that the degree of neutralization would be 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 200 r/min (peripheral speed of 63 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 maintained at 73° C. to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30°C while stirring at 280 r/min (peripheral speed of 88 m/min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid X-1 was obtained. Table 3 shows the volume-median particle size ( _D50 ) and CV value of the obtained resin particles.

Production Examples X2 to X8 (Production of Resin Particle Dispersions X-2 to X-8)
Resin particle dispersions X-2 to X-8 were obtained in the same manner as in Production Example X1, except that the resins used and the amount ratio (the total amount of the resins was the same) were changed as shown in Table 3. Table 3 shows the volume-median particle size ( _D50 ) and CV value of the obtained resin particles.

Production Example X9 (Production of Resin Particle Dispersion Liquid X-9)
A resin particle dispersion liquid X-9 was obtained in the same manner as in Production Example X1, except that the crystalline resin was not used and the amount of the amorphous resin A-1 was changed to 300 g and the amount of methyl ethyl ketone was changed to 360 g. Table 3 shows the volume-median particle size ( _D50 ) and CV value of the obtained resin particles.

Production Example Z1 (Production of Resin Particle Dispersion Z-1)
200 g of amorphous resin A-8 and 200 g of methyl ethyl ketone are placed 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 inlet tube, and the resin is heated at 73 ° C. for 2 hours. was dissolved. A 5 mass % sodium hydroxide aqueous solution was added to the obtained solution so that the degree of neutralization was 60 mol % with respect to the acid value of the amorphous resin A-8, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73° C. and stirring at 280 r/min (peripheral speed of 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 maintained at 73° C. to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30° C. while stirring at 280 r/min (peripheral speed of 88 m/min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid Z-1 was obtained. The volume-median particle size ( _D50 ) of the obtained resin particles was 0.09 μm, and the CV value was 23%.

[Production of Wax Particle Dispersion]
Production Example D11 (Production of wax particle dispersion D1-1)
120 g of deionized water, 86 g of resin particle dispersion Z-1, and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75 ° C.) were added to a beaker with an internal volume of 1 L, and the temperature was adjusted to 90 to 95 ° C. The mixture was melted while maintaining the temperature at 200°C and stirred to obtain a molten mixture.
While maintaining the temperature of the resulting molten mixture at 90 to 95 ° C., using an ultrasonic homogenizer "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.), dispersion treatment was performed for 40 minutes, and then cooled to room temperature (20 ° C.). cooled. Deionized water was added to adjust the solid content concentration to 20 mass % to obtain wax particle dispersion D1-1. Table 4 shows the volume median particle size _D50 and CV values of the wax particles in the dispersion.

Production Examples D12, D21, D22 (Production of Wax Particle Dispersions D1-2, D2-1, D2-2)
A wax particle dispersion was obtained in the same manner as in Production Example D11, except that the type of wax used was changed as shown in Table 4. Table 4 shows the volume median particle size ( _D50 ) and CV value of the wax particles in the dispersion.

[Production of colorant particle dispersion]
Production Example C1 (Production of Colorant Particle Dispersion C-1)
In a beaker with an internal volume of 1 L, cyan pigment "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd., copper phthalocyanine pigment) 100 g, polyoxyethylene (distyrenated phenyl) ether "Emulgen A-60" (manufactured by Kao Corporation, Nonionic surfactant, average added mole number of polyoxyethylene is 13) 35g and deionized water 300g are mixed and homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kika Kogyo Co., Ltd.). After dispersing for 1 hour at a stirring blade rotation speed of 8000 rpm at room temperature using "Microfluidizer M-110EH" (manufactured by Microfluidics), after 15 PASS treatment at a pressure of 150 MPa, pass through a 200 mesh filter, Colorant particle dispersion C-1 was obtained by adding deionized water so that the solid content concentration was 24% by mass. The volume-median particle diameter ( _D50 ) of the obtained colorant particles was 0.18 μm, and the CV value was 25%.

[Toner manufacturing]
Example 1 (Preparation of Toner 1)
500 g of Resin Particle Dispersion X-1, 49 g of Wax Particle Dispersion D1-1, and 49 g of Wax Particle Dispersion D2-1 were placed in a four-necked flask with an internal volume of 2 L equipped with a dehydration tube, a stirrer and a thermocouple. , 56 g of the colorant particle dispersion C-1, and 10 g of a 10% by weight aqueous solution of polyoxyethylene (50) lauryl ether "Emulgen 150" (manufactured by Kao Corporation, nonionic surfactant) were mixed at a temperature of 25°C. did. Next, while stirring the mixture, an aqueous solution of 35 g of ammonium sulfate dissolved in 512 g of deionized water was added with a 4.8% by mass aqueous potassium hydroxide solution to adjust the pH to 8.4. Then, the temperature was raised to 60° C. over 2 hours and maintained at 60° C. until the volume median particle size (D ₅₀ ) of the aggregated particles reached 5.2 μm to obtain a dispersion of aggregated particles. .
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate "Emal E-27C" (manufactured by Kao Corporation, an anionic surfactant, effective concentration of 27% by mass), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol/L sulfuric acid aqueous solution was added. After that, the temperature was raised to 77° C. over 1 hour, and the temperature was maintained at 77° C. until the circularity reached 0.965, thereby obtaining a dispersion liquid of fused particles in which aggregated particles were fused.
The fused particle dispersion thus obtained 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. Thereafter, vacuum drying was performed at 33° C. for 24 hours using a vacuum constant temperature dryer “DRV622DA” (manufactured by ADVANTEC) to obtain toner particles. Table 5 shows the physical properties of the obtained toner particles.
100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 0.04 μm), and hydrophobic silica “Cabosil (registered trademark) TS720” (Cabot Japan Co., Ltd. Toner 1 was obtained by adding 1.0 part by mass of the toner (manufactured by the company, number average particle diameter: 0.012 μm) into a Henschel mixer, stirring, and passing it through a 150-mesh sieve. Table 5 shows the evaluation results of Toner 1 obtained.

Examples 2 to 8, 13, 14, Comparative Example 1 (Preparation of toners 2 to 8, 13, 14, 51)
Toners 2 to 8, 13, 14, and 51 were obtained in the same manner as in Example 1, except that the types of resin particle dispersion and release agent particle dispersion used were changed as shown in Table 5. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 9 (Preparation of Toner 9)
Toner 9 was obtained in the same manner as in Example 1, except that the amount of wax particle dispersion D1-1 used was changed to 28 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 10 (Preparation of Toner 10)
Toner 10 was obtained in the same manner as in Example 1, except that the amount of wax particle dispersion D1-1 used was changed to 14 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 11 (Preparation of Toner 11)
Toner 11 was obtained in the same manner as in Example 1, except that the amount of wax particle dispersion D2-1 used was changed to 28 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 12 (Preparation of Toner 12)
Toner 12 was obtained in the same manner as in Example 1 except that the amount of wax particle dispersion D1-1 used was changed to 28 g and the amount of wax particle dispersion D2-1 used was changed to 28 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 15 (Preparation of Toner 15)
A dispersion of aggregated particles was obtained in the same manner as in Example 1.
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate "Emal E-27C" (manufactured by Kao Corporation, an anionic surfactant, effective concentration of 27% by mass), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol/L sulfuric acid aqueous solution was added. Thereafter, the temperature was raised to 75° C. over 1 hour, and the temperature was maintained at 75° C. until the circularity reached 0.965, thereby obtaining a dispersion of fused particles in which aggregated particles were fused.
The fusible particle dispersion thus obtained was treated in the same manner as in Example 1 to obtain Toner 15. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 16 (Preparation of Toner 16)
A dispersion of aggregated particles was obtained in the same manner as in Example 1.
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate "Emal E-27C" (manufactured by Kao Corporation, an anionic surfactant, effective concentration of 27% by mass), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol/L sulfuric acid aqueous solution was added. Thereafter, the temperature was raised to 73° C. over 1 hour, and the temperature was maintained at 73° C. until the circularity reached 0.965, thereby obtaining a dispersion of fused particles in which aggregated particles were fused.
The fusible particle dispersion thus obtained was treated in the same manner as in Example 1 to obtain Toner 16. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 17 (Preparation of Toner 17)
A dispersion of aggregated particles was obtained in the same manner as in Example 1.
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate "Emal E-27C" (manufactured by Kao Corporation, an anionic surfactant, effective concentration of 27% by mass), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol/L sulfuric acid aqueous solution was added. After that, the temperature was raised to 88° C. over 1 hour, and the temperature was maintained at 88° C. until the circularity reached 0.965, thereby obtaining a dispersion of fused particles in which aggregated particles were fused.
The fusible particle dispersion thus obtained was treated in the same manner as in Example 1 to obtain Toner 17. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 18 (Preparation of Toner 18)
A dispersion of aggregated particles was obtained in the same manner as in Example 1.
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate "Emal E-27C" (manufactured by Kao Corporation, an anionic surfactant, effective concentration of 27% by mass), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol/L sulfuric acid aqueous solution was added. Thereafter, the temperature was raised to 90° C. over 1 hour, and the temperature was maintained at 90° C. until the circularity reached 0.965, thereby obtaining a dispersion liquid of fused particles in which aggregated particles were fused.
The fusible particle dispersion thus obtained was treated in the same manner as in Example 1 to obtain Toner 18 . Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Comparative Example 2 (Preparation of Toner 52)
Toner 52 was obtained in the same manner as in Example 1, except that wax particle dispersion D1-1 was not used. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Comparative Example 3 (Preparation of Toner 53)
Toner 53 was obtained in the same manner as in Example 1, except that wax particle dispersion D2-1 was not used. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

As can be seen from the results in Table 5, the toners of Examples 1 to 18 are superior to the toners of Comparative Examples 1 to 3 in the image density of the printed matter and the hot offset resistance.

Claims (5)

An amorphous resin A having a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxyl group and a polyester resin segment, a crystalline resin B, a wax D1, a wax D2, and a colorant, wherein the wax D1 is lower than the melting point Tm2 of the wax D2, and the difference between the melting point Tm1 of the wax D1 and the melting point Tm2 of the wax D2 is 5° C. or more , wherein the crystalline resin B has a carbon number A polyhydric alcohol component containing 80 mol% or more of an α,ω-aliphatic diol having 4 to 16 carbon atoms and a polycarboxylic acid component containing 80 mol% or more of an aliphatic saturated dicarboxylic acid having 8 to 16 carbon atoms. It is a condensate, the content of the amorphous resin A in the binder resin is 60% by mass or more and 80% by mass or less, and the content of the crystalline resin B is 20% by mass or more and 40 % by mass in the binder resin. Toner, which is below. 2. The toner according to claim 1, wherein the difference between the melting point Tm1 of the wax D1 and the melting point Tm2 of the wax D2 is 10[deg.] C. or more. 3. The toner according to claim 1, wherein the wax D1 is a hydrocarbon wax. The toner according to any one of claims 1 to 3, wherein the wax D2 is a hydrocarbon wax. The toner according to any one of claims 1 to 4, wherein the coloring agent is coloring agent particles obtained by mixing the coloring agent and a compound represented by the following formula (1).

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