JP2023098415A - Manufacturing method of toner for electrostatic charge image development - Google Patents

Abstract

To provide a manufacturing method of toner for electrostatic charge image development which has the narrow toner particle grain size distribution, exhibits the high electrification characteristic even after storage under a high-temperature and high-humidity environment, can obtain a printed matter with the high image density, and suppress the occurrence of fogging in printing of an image under the high-temperature and high-humidity environment.SOLUTION: There is provided a manufacturing method of toner for electrostatic charge image development including the steps 1-3. The step 1 is the step of mixing a polyester resin A and an addition polymer E to obtain an aqueous dispersion of resin particles X including the polyester resin A and the addition polymer E. The step 2 is the step of aggregating the resin particles X in an aqueous medium to obtain aggregated particles. The step 3 is the step of fusing the aggregated particles obtained in the step 2 to obtain fused particles. The addition polymer E is the addition polymerization product of the raw material monomer including the addition polymerizable monomer having the styrene-based compound and the polyalkylene oxide group.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an electrostatic charge image developing toner used for developing a latent image formed in an electrophotography method, an electrostatic recording method, an electrostatic printing method, or the like.

In the field of electrophotography, with the development of electrophotographic systems, there is a demand for the development of electrophotographic toners capable of achieving high image quality and high speed. As a method of obtaining toner with narrow particle size distribution, small particle size, and fixability that can be used at high speeds, fine resin particles are aggregated and fused in an aqueous medium. 2. Description of the Related Art So-called chemical toners are produced by aggregation fusion methods (emulsion aggregation method, aggregation coalescence method) to obtain toner.
Chemical toners can be produced by aggregating fine particles in water, such as by lowering the glass transition temperature of the resin used in the core and forming a shell with a resin having a high glass transition temperature. While it is possible to achieve control of the toner structure, there is a problem that the chargeability tends to decrease due to the influence of the surfactant required during production.

In response to such problems, Patent Document 1 discloses a toner containing a binder resin, a colorant and a nonionic surfactant, wherein the nonionic surfactant comprises an oxyethylene group and an oxypropylene group. and the ratio of the number of moles of oxypropylene groups (PO) to the number of moles of oxyethylene groups (EO) (PO/EO) is 0.01 or more and 5.00 or less, and methanol is added to 1 g of the toner. The content of the nonionic surfactant on the surface of the extracted toner is defined as A (μg/g). is defined as B (m ² /g), a toner characterized by having a ratio (A/B) of 100 μg/m ² or more and 9000 μg/m ² or less.

JP 2011-257750 A

In recent years, the export of domestically manufactured toner cartridges and printers has increased, so the toner is required to have performance that can withstand the transportation environment on ships, that is, the high temperature and high humidity environment that far exceeds the normal usage environment. It became so. As a result of studies by the present inventors, when a surfactant is used in the production of a chemical toner, the surfactant is exposed on the surface of the toner particles in a high-temperature, high-humidity environment such as a transportation environment on a ship. It was found that the amount of charge was greatly reduced and printing troubles such as fogging occurred. Also, even with a toner containing a small amount of nonionic surfactant as described in Japanese Patent Laid-Open No. 2002-200011, the decrease in charge can be suppressed in a normal use environment. It was found that exposure of the surface active agent to the surface of the toner particles significantly reduces the amount of charge, resulting in printing troubles such as fogging. On the other hand, if a chemical toner is produced without using any surfactant in order to completely suppress the decrease in the charge amount and the exposure of the surfactant to the surface of the toner particles in a high-temperature and high-humidity environment, It has been found that, due to insufficient particle stability, print image quality is greatly reduced due to problems such as generation of coarse particles and broadening of particle size distribution.
The toner particles of the present invention have a narrow particle size distribution, exhibit high chargeability even after being stored in a high-temperature and high-humidity environment, provide printed matter with a high image density, and are suitable for printing images in a high-temperature and high-humidity environment. The present invention relates to a method for producing a toner for developing an electrostatic charge image that suppresses the occurrence of fogging.

The present inventors found that by using a polyester resin and an addition polymer having a specific structure as a binder resin, coarse particles are generated and the particle size distribution is broadened even if the amount of surfactant used is reduced. The present inventors have found a method for producing a toner for developing an electrostatic charge image, which is capable of obtaining an image of good image quality even after being stored under high temperature and high humidity conditions.
The present invention relates to the following [1].
[1] A method for producing a toner for developing an electrostatic charge image, comprising steps 1 to 3 below,
Step 1: Mix the polyester resin A and the addition polymer E to obtain an aqueous dispersion of resin particles X containing the polyester resin A and the addition polymer E Step 2: Resin particles X in an aqueous medium Aggregate to Obtain Aggregated Particles Step 3: Fusing the Aggregated Particles Obtained in Step 2 to Obtain Fused Particles The addition polymer E is an addition polymerizable monomer having a styrene compound and a polyalkylene oxide group. A method for producing a toner for electrostatic charge image development, which is an addition polymer of raw material monomers containing

According to the present invention, the toner particles have a narrow particle size distribution, exhibit high chargeability even after being stored in a high-temperature and high-humidity environment, obtain printed matter with a high image density, and print images in a high-temperature and high-humidity environment. Provided is a method for producing a toner for developing an electrostatic charge image that suppresses the occurrence of fogging in .

[Manufacturing Method of Toner for Developing Electrostatic Charge Image]
The method for producing the toner for electrostatic charge image development of the present invention includes a step of mixing a polyester resin A and an addition polymer E to obtain an aqueous dispersion of resin particles X containing the polyester resin A and the addition polymer E. 1. It includes step 2 of aggregating resin particles X in an aqueous medium to obtain aggregated particles, and step 3 of fusing the aggregated particles obtained in step 2 to obtain fused particles.
The addition polymer E is an addition polymer of raw material monomers containing a styrene compound and an addition polymerizable monomer having a polyalkylene oxide group.
By the above manufacturing method, the particles have a narrow particle size distribution, exhibit high chargeability even after being stored in a high-temperature and high-humidity environment, obtain printed matter with a high image density, and prevent fogging when printing images in a high-temperature and high-humidity environment. can be obtained.

According to the production method of the present invention, the toner particles have a narrow particle size distribution, exhibit high chargeability even after being stored in a high-temperature and high-humidity environment, obtain a printed matter with a high image density, and obtain an image in a high-temperature and high-humidity environment. Although the reason why a toner for developing an electrostatic charge image (hereinafter also simply referred to as "toner") capable of suppressing the occurrence of fogging in printing is obtained is not clear, the following may be considered.
Surfactants have the function of stabilizing the dispersion of fine polyester particles in water, and are indispensable compounds for the production of chemical toners by the emulsion aggregation method. However, since surfactants are generally water-soluble, they have high electrical conductivity. It is considered that the charge leaks during charging starting from the activator. As a result of the studies by the present inventors, it was found that, in the production process of chemical toner, the surfactant used for stabilizing the system, particularly in the aggregating process of aggregating resin fine particles, greatly affects the chargeability of the resulting toner. I found out.

As a result of intensive studies on improvement measures, the present inventors found that the addition polymer E, which is an addition polymer of raw material monomers containing a styrene compound and an addition polymerizable monomer having a polyalkylene oxide group, stabilizes the dispersibility of fine resin particles. It was found that the use of surfactants in the flocculation process can be greatly reduced. The resin particles X containing the addition polymer E and the polyester resin A have a composite structure in which the hydrophobic styrenic compound-derived sites of the addition polymer E are adsorbed to the hydrophobic sites of the polyester resin A. It is thought that the sites derived from the addition polymerizable monomer having a hydrophilic polyalkylene oxide group are oriented toward the water layer in the water-containing dispersion medium. Therefore, the resin particles X are considered to be able to exist stably in water without adding a surfactant due to the steric stabilization effect of the polyalkylene oxide group, and even in the process of obtaining agglomerated particles, they do not become coarse and relatively Aggregated particles having a narrow particle size distribution are obtained, and the particle size distribution of the finally obtained toner particles is considered to be narrow. In addition, the toner containing toner particles obtained by aggregating and fusing the resin particles X does not contain a surfactant or contains a very small amount of a surfactant. Even when stored, the surfactant does not migrate to the surface of the toner and does not cause a decrease in the charge of the toner, so that a printed matter with a high image density can be obtained, and an image can be printed in a high-temperature and high-humidity environment. Stable printing performance with suppressed fogging.

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 in which no endothermic peak is observed or, if observed, the crystallinity index is 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.
With respect to hydrocarbon groups, references to parentheses "(iso or tertiary)" and "(iso)" mean both the presence and absence of these prefixes, and the absence of these prefixes. In some cases, the normal is shown.
"(Meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid.
"(Meth)acrylate" means at least one selected from acrylate and methacrylate.
A "(meth)acryloyl group" means at least one selected from an acryloyl group and a methacryloyl group.
"Styrenic compound" means unsubstituted or substituted styrene.
By "backbone" is meant the longest relatively connecting chain in the addition polymer.

[Step 1]
In step 1, a polyester resin A and an addition polymer E are mixed to obtain an aqueous dispersion of resin particles X containing the polyester resin A and the addition polymer E.

[Polyester resin A]
Polyester-based resin A (hereinafter also simply referred to as “resin A”) is, for example, a polyester-based resin containing a polycondensate of an alcohol component and a carboxylic acid component, and is preferably an amorphous polyester-based resin.
Examples of resin A include polyester resins and modified polyester resins. Modified polyester resins include, for example, urethane-modified polyester resins, epoxy-modified polyester resins, and composite resins containing polyester resin segments and addition polymerized resin segments. Among these, resin A is preferably a polyester resin and a composite resin.

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

（式中、ＯＲ^１及びＲ^２Ｏはオキシアルキレン基であり、Ｒ^１及びＲ^２はそれぞれ独立にエチレン基又はプロピレン基であり、ｘ及びｙはアルキレンオキシドの平均付加モル数を示し、それぞれ正の数であり、ｘとｙの和の値は、１以上、好ましくは１．５以上、更に好ましくは１．８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、更に好ましくは３以下、更に好ましくは２．５以下である）で表されるビスフェノールＡのアルキレンオキシド付加物である。

(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y represent the average number of moles of alkylene oxide added, each positive and the sum of x and y is 1 or more, preferably 1.5 or more, more preferably 1.8 or more, and 16 or less, preferably 8 or less, more preferably 4 or less, more preferably is 3 or less, more preferably 2.5 or less).

Examples of the alkylene oxide adduct of bisphenol A represented by formula (I) include a propylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(4-hydroxyphenyl)propane. and ethylene oxide adducts of. Among these, the propylene oxide adduct of bisphenol A is preferred.
In the alcohol component, the content of the alkylene oxide adduct of bisphenol A is preferably 80 mol% or more, more preferably 90 mol% or more, from the viewpoint of strengthening the hydrophobic interaction with the addition polymer E, and , 100 mol % or less, 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.
One or more of these alcohol components may be used.

Examples of the carboxylic acid component of resin A 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 99 mol% or less, more preferably It is 95 mol % or less, more preferably 93 mol % or less.

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

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, such as trimellitic acid or its anhydride.
When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid is preferably 1 mol% or more, more preferably 1.5 mol% or more, still more preferably 2 mol% or more, in the carboxylic acid component. mol % or more, and preferably 30 mol % or less, more preferably 20 mol % or less, still more preferably 15 mol % or less.
One or more of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group/OH group] is preferably 0.7 or more, more preferably 0.75 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.

When the resin A is a composite resin, the addition polymerized resin segment may be, for example, an addition polymer of raw material monomers containing styrene compounds.
Styrenic compounds include, for example, unsubstituted or substituted styrene. Examples of substituents for styrene 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 styrenic compound in the raw material monomers of the addition polymerized resin segment is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 75% by mass or more, and 100% by mass or less. , preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

Examples of raw material monomers other than styrene compounds include (meth)acrylic acid esters such as alkyl (meth)acrylate, benzyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate; olefins; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; . Among these, (meth)acrylic acid esters are preferred, and alkyl (meth)acrylates are more preferred.
The number of carbon atoms in the alkyl group in the alkyl (meth)acrylate is preferably 1 or more, more preferably 4 or more, still more preferably 6 or more, and is preferably 24 or less, more preferably 22 or less, and still more preferably 20. It is below.
Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, (iso- or tertiary) butyl (meth)acrylate, (meth)acrylate, ) (iso)amyl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, (meth)acrylic acid ( iso) dodecyl, (iso) palmityl (meth) acrylate, (iso) stearyl (meth) acrylate, (iso) behenyl (meth) acrylate and the like, preferably 2-ethylhexyl (meth) acrylate or ( Meth)stearyl acrylate, more preferably stearyl (meth)acrylate, still more preferably stearyl methacrylate.

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

The total amount of the styrenic compound and the (meth)acrylic acid ester in the raw material monomers of the addition polymerization resin segment is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably. is 100% by mass.

The composite resin preferably has structural units derived from bi-reactive monomers that are covalently bonded to the polyester resin segment and the addition polymerized resin segment.
The “structural unit derived from a bireactive monomer” means a unit obtained by reacting a functional group and an addition polymerizable group of a bireactive monomer.
Examples of addition polymerizable groups include carbon-carbon unsaturated bonds (ethylenically unsaturated bonds).
Examples of bi-reactive monomers include 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, from the viewpoint of reactivity, addition polymerizable monomers having at least one functional group selected from hydroxyl groups and carboxy groups are preferred, and addition polymerizable monomers having a carboxy group are more preferred.
Addition-polymerizable monomers having a carboxy group include, for example, acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred, from the viewpoint of reactivity in both polycondensation reaction and addition polymerization reaction.
When the bireactive monomer is an addition polymerizable monomer having a carboxy group, the amount of the structural unit derived from the bireactive monomer is preferably 1 mol part per 100 mol parts of the alcohol component of the polyester resin segment of the composite resin. Above, it is more preferably 5 mol parts or more, still more preferably 8 mol parts or more, and preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less.

The content of the polyester resin segment in the composite resin is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably 55% by mass or more with respect to the total amount of the polyester resin segment and the addition polymerized resin segment. Yes, and preferably 95% by mass or less, more preferably 85% by mass or less, and even more preferably 75% by mass or less. In addition, let the structural unit derived from a bi-reactive monomer be a polyester resin segment.

The content of the addition polymerized resin segment in the composite resin is preferably 5% by mass or more, more preferably 15% by mass or more, and still more preferably 25% by mass or more, based on the total amount of the polyester resin segment and the addition polymerized resin segment. and is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 45% by mass or less.

The amount of the structural unit derived from the bi-reactive monomer in the composite resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the polyester resin segment and the addition polymerized resin segment, It is more preferably 0.8% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 4% by mass or less.

The total amount of the polyester resin segment and the addition polymerized resin segment in the composite resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less, and , and more preferably 100% by mass.

The above amounts are calculated based on the ratio of the amounts of the polyester resin segment, raw material monomers for the addition polymerization resin segment, bi-reactive monomer, and radical polymerization initiator. Based on mass excluding mass. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is included in the addition polymerization resin segment in the calculation.

(Method for producing polyester resin A)
<Method for producing polyester resin>
When resin A is a polyester resin, resin A may be produced, for example, by polycondensing raw material monomers containing an alcohol component and a carboxylic acid component.

Polycondensation of the alcohol component and the carboxylic acid component is carried out, for example, in an inert gas atmosphere, if necessary, in the presence of an esterification catalyst, an esterification co-catalyst, a polymerization inhibitor, etc., at a temperature of about 120 ° C. or higher and 250 ° C. or lower. can be performed at a temperature of
Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and di(2-ethylhexanoate)tin (II), and titanium compounds such as titanium diisopropoxybis(triethanolamine). Esterification cocatalysts that can be used with the esterification catalyst include, for example, gallic acid (3,4,5-trihydroxybenzoic acid).
The amount of the esterification catalyst used is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total amount of the alcohol component (a) and the carboxylic acid component (b), which are raw material monomers of Resin A. be.
The amount of the esterification co-catalyst used is preferably 0.001 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass as the total of the alcohol component (a) and the carboxylic acid component (b).
Examples of polymerization inhibitors include radical polymerization inhibitors such as 4-tert-butylcatechol.
When a polymerization inhibitor is used, the amount of the polymerization inhibitor used is preferably 0.01 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the total amount of the alcohol component (a) and the carboxylic acid component (b). .

<Method for manufacturing composite resin>
When the resin A is a composite resin containing a polyester resin segment and an addition polymerized resin segment, for example, a step A of polycondensing an alcohol component and a carboxylic acid component, and adding a raw material monomer and a bireactive monomer for the addition polymerized resin segment. It may be produced by a method including the step B of polymerizing.
Process B may be performed after process A, process A may be performed after process B, or process A and process B may be performed simultaneously.
In step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, and then step B is carried out. A method of further advancing the polycondensation reaction with the carboxy group of the constituent site derived from the reactive monomer is preferred.

In step A, if necessary, polycondensation may be carried out using the esterification catalyst and the esterification co-catalyst described in the method for producing the polyester resin in the same amounts.
Further, when using a monomer having an unsaturated bond such as fumaric acid for polycondensation, if necessary, the polymerization inhibitor described in the method for producing the polyester resin may be used in the same amount. .
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

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

(Physical properties of polyester resin A)
The softening point of Resin A is preferably 70° C. or higher, more preferably 90° C. or higher, still more preferably 100° C. or higher, and preferably 140° C. or lower, more preferably 130° C. or lower, still more preferably 125° C. or lower. is.
The glass transition temperature of Resin A is preferably 30°C or higher, more preferably 35°C or higher, still more preferably 40°C or higher, and is preferably 80°C or lower, more preferably 75°C or lower, and still more preferably 70°C. It is below.

The acid value of Resin A is preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, still more preferably 8 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, and further preferably Preferably, it is 30 mgKOH/g or less.

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

[Addition polymer E]
Addition polymer E (hereinafter also simply referred to as "polymer E") is a styrene compound a (hereinafter also simply referred to as "monomer a") and an addition polymerizable monomer b having a polyalkylene oxide group (hereinafter simply referred to as " It is an addition polymer of raw material monomers containing (also referred to as "monomer b").

Raw material monomers for the polymer E include, in addition to the monomer a and the monomer b, preferably an addition polymerizable monomer c having an ionic group (hereinafter also simply referred to as "monomer c") and a macromonomer d (hereinafter simply referred to as "monomer d (also referred to as "), more preferably both monomer c and monomer d.

Monomer a includes, for example, substituted or unsubstituted styrene. Examples of substituents for styrene include alkyl groups having 1 to 5 carbon atoms, halogen atoms, alkoxy groups having 1 to 5 carbon atoms, sulfo groups, and salts thereof. Monomer a is preferably nonionic.
The molecular weight of monomer a is preferably 1,000 or less, more preferably 800 or less, still more preferably 500 or less, still more preferably 300 or less, and preferably 80 or more, more preferably 90 or more, further preferably 100 That's it.
Examples of the monomer a include styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts thereof. Among these, styrene is preferred.
From the viewpoint of strengthening the hydrophobic interaction with resin A, the amount of monomer a is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass or more in the raw material monomers of polymer E. and preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less.

The average number of moles of alkylene oxide added to the polyalkylene oxide group of the monomer b is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 30 or less, more preferably 20 or less, and further It is preferably 10 or less.
Monomer b is preferably nonionic.
Examples of the monomer b include polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; alkoxy polyalkylene glycol (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate; phenoxy ( ethylene glycol-propylene glycol copolymerization) (meth)acrylates and other aryloxypolyalkylene glycol (meth)acrylates, and from the viewpoint of obtaining a steric stabilization effect for the resin particles X in an aqueous medium, alkoxypolyalkylene glycols are preferred. It is a (meth)acrylate.
From the viewpoint of improving the dispersion stability of the resin particles X, the amount of the monomer b is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more in the raw material monomers of the polymer E. Yes, preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

The ionic group in the monomer c means a group that dissociates ions in water.
The ionic group includes, for example, a carboxy group, a sulfo group, a phosphate group, an amino group, or salts thereof.
The ionic group is preferably an anionic group. As an anionic group, an acidic group or a salt thereof is preferable, a carboxy group, a sulfo group or a salt thereof is more preferable, and a carboxy group or a salt thereof is still more preferable.
Addition-polymerizable monomers having a carboxy group include, for example, (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, and 2-methacryloyloxymethylsuccinic acid.
Among these, addition-polymerizable monomers having an anionic group are preferred, (meth)acrylic acid is more preferred, and methacrylic acid is even more preferred.
When the monomer c is contained, the amount of the monomer c is preferably 2% by mass or more, more preferably 5% by mass or more, in the raw material monomers of the polymer E, from the viewpoint of improving the dispersion stability of the resin particles X. It is preferably 7% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

The monomer d includes, for example, a styrene-based compound polymer having an addition-polymerizable functional group at one end (hereinafter also referred to as "styrene-based macromonomer"). Examples of addition polymerizable functional groups include vinyl groups, allyl groups, and (meth)acryloyl groups. Among these, a (meth)acryloyl group is preferred.
As the styrenic compound in the monomer d, styrene is preferred.
The number average molecular weight of the monomer d is preferably 1,000 or more and 10,000 or less. The number average molecular weight is measured by gel permeation chromatography using chloroform containing 1 mmol/L of dodecyldimethylamine as a solvent, using polystyrene as a standard substance.
Examples of commercially available styrene-based macromonomers include "AS-6", "AS-6S", "AN-6", "AN-6S", "HS-6", and "HS-6S" (above, manufactured by Toagosei Co., Ltd.) and the like.

When the monomer d is contained, the amount of the monomer d is preferably 3% by mass or more, more preferably 6% by mass or more, in the raw material monomers of the polymer E from the viewpoint of strengthening the hydrophobic interaction with the resin A, More preferably 10% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.
In the raw material monomers of the polymer E, the total amount of the monomer a and the monomer d is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably from the viewpoint of strengthening the hydrophobic interaction with the resin A. It is 50% by mass or more, and preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.

Furthermore, as raw material monomers of the polymer E, addition polymerizable monomers (other monomers) other than the monomers a to d may be contained.
Other monomers include, for example, alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms (preferably 6 to 18 carbon atoms), benzyl (meth)acrylate, aromatics such as phenoxyethyl (meth)acrylate. group-containing (meth)acrylates.
When other monomers are contained, the amount of the other monomers is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 10% by mass, in the raw material monomers of polymer E. % by mass or less, more preferably 5% by mass or less.
(Method for producing addition polymer E)

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

(Physical properties of addition polymer E)
From the viewpoint of further improving the image density, the weight average molecular weight of the polymer E is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 20,000 or more, still more preferably 40,000 or more. It is preferably 50,000 or more, and preferably 200,000 or less, more preferably 90,000 or less, even more preferably 60,000 or less, and even more preferably 53,000 or less. The weight average molecular weight can be measured by the method described in Examples.

[Method for Producing Aqueous Dispersion of Resin Particles X]
The aqueous dispersion of the resin particles X is obtained by mixing and dispersing the resin A and the polymer E in an aqueous medium and coalescing them.
The aqueous medium preferably contains water as a main component, and from the viewpoint of improving the dispersion stability of the aqueous dispersion of resin particles X and from the viewpoint of environmental friendliness, the content of water in the aqueous medium is preferably It is 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and is 100% by mass or less, still more preferably 100% by mass. As water, deionized water or distilled water is preferred. Components other than water that can be contained in the aqueous medium include, for example, alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 total carbon atoms such as acetone and methyl ethyl ketone; and cyclic ethers such as tetrahydrofuran. Dissolving organic solvents are included. Among these, methyl ethyl ketone is preferred.

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 to the organic solvent solution of the resin. Neutralizing agents include, for example, basic substances. Basic substances include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The degree of neutralization of the resin contained in the resin particles X is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and even more preferably 40 mol% or more. is 100 mol % or less, more preferably 80 mol % or less, still more preferably 70 mol % or less.
The degree of neutralization of the resin contained in the resin particles X can be determined by the following formula.
Degree of neutralization (mol%) = [{neutralizing agent added mass (g)/neutralizing agent equivalent}/[{weighted average acid value of resin contained in resin particles X (mgKOH/g) x resin particles X Mass of resin contained in (g)} / (56 × 1000)]] × 100

While stirring the organic solvent solution of the resin or the 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 of the resin when the aqueous medium is added is preferably equal to or higher than the glass transition temperature of the resin having the highest glass transition temperature among the resins, and more preferably. is 50°C or higher, more preferably 60°C or higher, even more preferably 70°C or higher, and is preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 80°C or lower.

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

From the viewpoint of the stability of the resin particles X in the aqueous dispersion, the content of the polymer E in the resin particles X is preferably 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably 2% by mass. % by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

The mass ratio of the polymer E to the resin A in the resin particles X [polymer E/resin A] is from the viewpoint of enhancing the hydrophobic interaction between the resin A and the polymer E, and From the viewpoint of stability at , it is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.025 or more, and preferably 0.1 or less, more preferably 0.08 or less, More preferably, it is 0.07 or less.

The volume-median particle size _D50 of the resin particles X in the aqueous dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, and still more preferably 0, from the viewpoint of obtaining a toner capable of obtaining high-quality images. 0.1 μm or more, and preferably 0.5 μm or less, more preferably 0.25 μm or less, and even more preferably 0.18 μm or less.
The CV value of the resin particles X in the aqueous dispersion is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, from the viewpoint of obtaining a toner capable of obtaining high-quality images. Preferably it is 30% or less.
The volume-median particle size _D50 and CV value are determined by the methods described in Examples below.

The resin particles X may further contain a crystalline polyester resin C when the polyester resin A is amorphous. The resin particles X further containing the crystalline polyester resin C can be produced according to the above method. The preferred ranges of the volume-median particle size _D50 and the CV value of the resin particles X further containing the crystalline polyester resin C are the same as those described above.
Moreover, it is preferable that the resin particles X do not contain a coloring agent.

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

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

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

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

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

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

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

The method for producing Resin C includes, for example, the same method as for Resin A, which is the polyester resin described above.

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

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

From the viewpoint of thermal responsiveness of the toner, the content of the resin C is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass with respect to the total amount of the resin components of the resin particles X. It is the above and is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and even more preferably 25% by mass or less.
The mass ratio of resin C to resin A in resin particles X [resin C/resin A] is preferably 0.03 or more, more preferably 0.05 or more, and still more preferably 0, from the viewpoint of thermal responsiveness of the toner. 0.07 or more, and preferably 0.50 or less, more preferably 0.40 or less, and even more preferably 0.30 or less.

[Step 2]
In step 2, resin particles X are aggregated in an aqueous medium to obtain aggregated particles 1 . Here, in addition to the resin particles X, it is preferable to further aggregate at least one of the colorant and the release agent. More preferably, these particles are aggregated by mixing with a liquid and/or a release agent particle dispersion containing release agent particles.

[Coloring agent]
As the colorant, all dyes, pigments, etc. used as colorants for toners can be used.
Examples of colorants include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, and disazo yellow. mentioned. The toner may be black toner or color toner other than black.
The content of the colorant in the toner particles is preferably 3% by mass or more, more preferably 5% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass. % or less.

(Colorant particle dispersion)
The colorant particle dispersion is preferably obtained by dispersing the colorant and the aqueous medium using a dispersing machine such as a homogenizer or an ultrasonic dispersing machine. From the viewpoint of improving the dispersion stability of the colorant, the dispersion is preferably carried out in the presence of a surfactant or an addition polymer.

Examples of surfactants that improve the dispersion stability of colorants include nonionic surfactants, anionic surfactants, and cationic surfactants. Therefore, nonionic surfactants are preferred. Nonionic surfactants include, for example, polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, and polyoxyalkylene aryl ethers. Among these, polyoxyethylene aryl ethers are preferred, and polyoxyethylene distyrenated phenyl ether is more preferred.

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

As the addition polymer for improving the dispersion stability of the colorant, the same addition polymer as the above addition polymer E can be used.
In the colorant particle dispersion, the mass ratio of the colorant and the addition polymer (colorant/addition polymer) is preferably 50/50 or more, more preferably 60, from the viewpoint of improving the dispersion stability of the colorant. /40 or more, more preferably 70/30 or more, more preferably 75/25 or more, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less.
When a dispersion of colorant particles is produced from a colorant and an addition polymer, it can be produced, for example, by the production method described in paragraphs [0067] to [0076] of WO 2019/156231.

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

The volume median particle size _D50 of the colorant particles is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.1 μm or more, from the viewpoint of improving image density. It is 0.4 μm or less, more preferably 0.3 μm or less, still more preferably 0.2 μm or less.
From the viewpoint of improving image density, the CV value of the colorant particles is preferably 10% or more, more preferably 20% or more, and is preferably 45% or less, more preferably 40% or less, and still more preferably 35%. % or less.
The volume median particle size _D50 and CV values of the colorant particles are determined by the methods in the Examples.

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

〔Release agent〕
Release agents include, for example, polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sasol wax; and oxides thereof; carnauba wax. , montan waxes or their deoxidized waxes, ester waxes such as fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. These may use 1 type(s) or 2 or more types.

The melting point of the release agent is preferably 60° C. or higher, more preferably 70° C. or higher, and is preferably 160° C. or lower, more preferably 140° C. or lower, still more preferably 120° C. or lower, and still more preferably 100° C. or lower. is.
The content of the release agent in the toner particles is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass. % by mass or less, more preferably 12% by mass or less.

(Releasing agent particle dispersion)
The release agent particle dispersion can be obtained by using a surfactant, but from the viewpoint of reducing the content of the surfactant contained in the toner, the release agent and the resin particles S are mixed. It is preferable to obtain By preparing release agent particles using a release agent and resin particles S, the release agent particles are stabilized by the resin particles S, and the release agent can be dispersed in an aqueous medium without using a surfactant. Dispersion becomes possible. It is considered that the release agent particle dispersion liquid has a structure in which a large number of resin particles S adhere to the surface of the release agent particles.

The resin constituting the resin particles S in which the release agent is dispersed is preferably a polyester-based resin, and it is more preferable to use a composite resin D having a polyester resin segment and an addition polymerized resin segment. As the composite resin D, the same composite resin as the resin A can be used.

The softening point of composite resin D is preferably 70°C or higher, more preferably 80°C or higher, still more preferably 85°C or higher, and is preferably 140°C or lower, more preferably 120°C or lower, and still more preferably 100°C. It is below.
The glass transition temperature of composite resin D is preferably 30° C. or higher, more preferably 35° C. or higher, and still more preferably 40° C. or higher, and from the viewpoint of further improving low-temperature fixability, it is preferably 80° C. or lower, more preferably 80° C. or lower. It is preferably 70° C. or lower, more preferably 60° C. or lower.
The acid value of Composite Resin D is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g, from the viewpoint of obtaining fine resin particles and obtaining a fine release agent particle dispersion. Above, more preferably 20 mgKOH/g or more, preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, still more preferably 30 mgKOH/g or less.
The softening point, glass transition temperature, and acid value of the composite resin D can be appropriately adjusted depending on the type and amount of the raw material monomer used, and the production conditions such as the reaction temperature, reaction time, and cooling rate. The value is determined by the method described in Examples.
When two or more composite resins D are used in combination, the softening point, glass transition temperature and acid value obtained as a mixture thereof are preferably within the above ranges.

The dispersion liquid of resin particles S can be obtained, for example, by the phase inversion emulsification method shown in the method for producing an aqueous dispersion of resin particles X described above.
The volume-median particle size _D50 of the resin particles S is preferably 0.01 μm or more, more preferably 0.03 μm or more, and preferably 0.3 μm or less, from the viewpoint of the dispersion stability of the release agent particles. , and more preferably 0.2 μm or less.
From the viewpoint of the dispersion stability of the release agent particles, the CV value of the resin particles S is preferably 10% or more, more preferably 15% or more, and preferably 40% or less, more preferably 35% or less. More preferably, it is 30% or less.
The volume-median particle diameter _D50 and CV value of the resin particles S are measured by the methods described in Examples.

The releasing agent particle dispersion is obtained, for example, by dispersing the releasing agent, resin particle S dispersion, and optionally an aqueous medium at a temperature equal to or higher than the melting point of the releasing agent in a homogenizer, a high-pressure disperser, or an ultrasonic disperser. obtained by dispersing using a dispersing machine such as
The heating temperature during dispersion is preferably the melting point of the releasing agent or higher and 80°C or higher, more preferably 85°C or higher, and still more preferably 90°C or higher, and preferably softens the resin contained in the resin particles S. It is less than 10°C higher than the point and 100°C or less, more preferably 98°C or less, still more preferably 95°C or less.

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

The volume-median particle size _D50 of the release agent particles is preferably 0.05 μm or more, more preferably 0.1 μm or more, and still more preferably 0.2 μm or more, from the viewpoint of obtaining uniform aggregated particles 1 by aggregation. , and preferably 1 μm or less, more preferably 0.8 μm or less, and even more preferably 0.6 μm or less.
The CV value of the release agent particles is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and preferably 40% or less, more preferably 35% or less, further preferably 30%. % or less.
The volume-median particle diameter _D50 and CV value of the release agent particles are measured by the methods described in Examples.

Aggregated particles also contain additives such as charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleaning improvers. You can stay.

[Flocculant]
In the step of aggregating the resin particles, it is preferable to add an aggregating agent from the viewpoint of efficient aggregation.
Examples of flocculants include cationic surfactants such as quaternary salts, organic flocculants such as polyethyleneimine, and inorganic flocculants. Examples of inorganic flocculants include inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate; inorganic ammonium salts such as ammonium sulfate, ammonium chloride and ammonium nitrate; and divalent or higher metal complexes. .
From the viewpoint of improving cohesiveness and obtaining uniform aggregated particles 1, a monovalent to pentavalent inorganic flocculant is preferable, and a monovalent to divalent inorganic metal salt and inorganic ammonium salt are more preferable, and an inorganic ammonium salt. is more preferred, and ammonium sulfate is even more preferred.

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

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.

The volume-median particle diameter _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, further preferably 7 μm or less. be.

In step 2, after the step of aggregating resin particles X and before the step of fusing resin particles X, resin particles containing polyester-based resin B (hereinafter also simply referred to as "resin B") in aggregated particles 1 obtained. A step of adhering Y to obtain aggregated particles 2 may be included. By including the step of aggregating the resin particles Y, toner particles having a core-shell structure can be obtained.
Here, as the resin B, the above resin A is exemplified, and it is preferably amorphous. The resin particles Y are obtained as an aqueous dispersion by the same method as the method for producing the aqueous dispersion of the resin particles X described above.
Further, when the step 2 has a step of obtaining the aggregated particles 2, it is preferable to stop the aggregation when the aggregated particles 2 have grown to an appropriate particle size as toner particles in the step, and the above aggregation terminating agent is added. A method of stopping aggregation by addition is preferred.
The mass ratio of resin particles Y to the mass of aggregated particles 1 [resin particles Y/aggregated particles 1] is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably It is 0.05 or more, and preferably 0.3 or less, more preferably 0.25 or less, and still more preferably 0.20 or less.

The amount of the surfactant used in step 2 is preferably less than 5 parts by mass, more preferably 4 parts by mass with respect to 100 parts by mass of the resin particles X, from the viewpoint of reducing the content of the surfactant contained in the toner. parts, more preferably less than 3.5 parts by mass.

[Aggregation terminating agent]
Before the aggregated particles are obtained in step 2 and fused together in step 3, an aggregation terminator may be added from the viewpoint of reliably preventing unnecessary aggregation.
As the aggregation terminator, a surfactant is preferred, and an anionic surfactant is more preferred. Examples of anionic surfactants include alkylbenzenesulfonates, alkylsulfates, alkylethersulfates, polyoxyalkylene alkylethersulfates, arylsulfonates, arylsulfonic acid formalin condensates, and the like, preferably It is an alkali metal salt of an arylsulfonic acid formalin condensate, more preferably a sodium salt of a naphthalenesulfonic acid formalin condensate. These may be used alone or in combination of two or more. The aggregation terminator may be added in the form of an aqueous solution.
The addition amount of the aggregation terminator is preferably 1 part by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the resin in the resin particles, from the viewpoint of reliably preventing unnecessary aggregation, and , preferably 60 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, from the viewpoint of reducing the residual amount in the toner.

[Step 3]
In step 3, for example, the aggregated particles 1 or 2 obtained in step 2 are fused in an aqueous medium to obtain fused particles.
In Step 3, from the viewpoint of improving the fusibility of the aggregated particles 1 or 2 and from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, a resin glass having the highest glass transition temperature of the aggregated particles is used. Hold at a temperature above the transition temperature.
From the viewpoint of improving the fusibility of the aggregated particles and improving the productivity of the toner, the holding temperature for fusing the aggregated particles is determined from the glass transition temperature of the resin having the highest glass transition temperature of the aggregated particles. preferably 2°C or higher, more preferably 3°C or higher, still more preferably 5°C or higher, and preferably 30°C or lower, more preferably 25°C or lower, even more preferably 20° C. higher temperature or less.
At that time, the time for holding at a temperature equal to or higher than the glass transition temperature of the resin having the highest glass transition temperature of the aggregated particles is preferably 1 minute or more, more preferably 1 minute or more, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. is 10 minutes or more, more preferably 30 minutes or more, and is preferably 240 minutes or less, more preferably 180 minutes or less, even more preferably 120 minutes or less, still more preferably 90 minutes or less.
In addition, it is preferable to hold at the above temperature until the desired degree of circularity is achieved.

The volume-median particle diameter _D50 of the fused particles obtained by fusion is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less. , and more preferably 7 μm or less.

The circularity of the fused particles obtained by fusion bonding is preferably 0.955 or more, more preferably 0.960 or more, still more preferably 0.965 or more, and preferably 0.990 or less, more preferably It is 0.985 or less, more preferably 0.980 or less.
It is preferable that the fusion-bonding is completed after reaching the above-mentioned preferable degree of circularity.
Circularity is measured by the method described in Examples.

[Post-treatment process]
A post-treatment step may be performed after the fusing step to obtain toner particles by isolating the fusing particles. Since the fused particles obtained in the fused step are present in the aqueous medium, it is preferable to perform solid-liquid separation first. A suction filtration method or the like is preferably used for the solid-liquid separation.
Washing is preferably performed after solid-liquid separation. At this time, since it is preferable to remove the added surfactant as well, it is preferable to wash with an aqueous medium at a temperature not higher than the cloud point of the surfactant. Washing is preferably performed multiple times.
Drying is then preferably carried out. Examples of the drying method include vacuum low temperature drying, vibrating fluidized drying, spray drying, freeze drying, and flash jet.

[Toner particles]
The volume-median particle diameter _D50 of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, or more, from the viewpoint of further improving the cleaning property of the toner. It is preferably 8 μm or less, more preferably 7 μm or less.

The circularity of the toner particles is preferably 0.955 or more, more preferably 0.960 or more, still more preferably 0.965 or more, and preferably 0.990 or less, more preferably 0.985 or less, and more preferably 0.985 or less. It is preferably 0.980 or less.

The CV value of the toner particles is preferably 10% or more, more preferably 15% or more, and still more preferably 18% or more from the viewpoint of improving toner productivity. It is preferably 40% or less, more preferably 35% or less, still more preferably 32% or less.
The volume-median particle size _D50 of the toner particles can be measured by the method described in the Examples.

[Electrostatic charge image developing toner]
The electrostatic charge image developing toner of the present invention contains toner particles.
Although the toner particles can be used as the toner as it is, it is preferable to use the toner after adding a fluidizing agent or the like as an external additive to the surface of the toner particles.

[External additive]
Examples of external additives include fine particles of inorganic materials such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and fine particles of polymers such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred. One type of external additive may be used alone, or two or more types may be used. Moreover, two or more kinds of hydrophobic silica having different particle sizes may be used.
When the toner particles are surface-treated using an external additive, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 100 parts by mass of the toner particles. It is 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and even more preferably 4 parts by mass or less.

Toners are used for electrostatic image development in electrophotographic printing. The toner can be used, for example, as a one-component developer or mixed with a carrier as a two-component developer.

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

[Measuring method]
The property values of the polyester resin, resin particles, toner, etc. were measured and evaluated by the following methods.
[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 Instrument Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan and cooled to 0 ° C. at a cooling rate of 10 ° C./min. bottom. 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 down 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 a crystalline resin, 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 point of intersection with the extended line of the baseline on the low temperature side was defined as the glass transition temperature.

[Acid value of resin]
The acid value of the resin was measured according to the neutralization titration method described in JIS K 0070:1992. However, a mixed solvent of acetone and toluene (acetone:toluene=1:1 (volume ratio)) was used as the measurement solvent.

[Melting point of release agent]
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.

[Volume-median particle size _D50 and CV value of resin particles, colorant particles, and release agent particles]
(1) Measuring device: Laser diffraction particle size measuring machine “LA-920” (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: A sample dispersion was placed in a measurement cell, distilled water was added, and the volume median particle diameter _D50 and the volume average particle diameter Dv 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 Dv) x 100

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

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

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

[Weight Average Molecular Weight of Addition Polymer]
Gel permeation chromatography [GPC apparatus "HLC-8320GPC" ( Tosoh Corporation), columns "TSKgel Super AWM-H", "TSKgel SuperAW3000", "TSKgel guardcolumn Super AW-H" (manufactured by Tosoh Corporation), flow rate: 0.5 mL / min], the molecular weight is known as a standard substance monodisperse polystyrene kit [PStQuick B (F-550, F-80, F-10, F-1, A-1000), PStQuick C (F-288, F-40, F-4, A-5000, A -500), manufactured by Tosoh Corporation].

[Charge amount under normal temperature and humidity]
At a temperature of 25° C. and a relative humidity of 50%, 2.1 g of toner and 27.9 g of silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size: 40 μm) were poured into a 50 mL cylindrical polypropylene bottle (Nikko Hansen Co., Ltd.). ) and mixed for 10 minutes at 250 r/min using a ball mill. After that, the charge amount was measured under the following conditions using "q/m-meter" (manufactured by Epping).
・Mesh size: 635 mesh (opening: 24 μm, made of stainless steel)
・Soft blow: blow pressure (1000V)
・Suction time: 90 seconds The amount of charge is obtained by the following formula, and the larger the absolute value of the numerical value, the better the chargeability.
Charge amount (μC/g)=Total amount of electricity (μC) after 90 seconds/Attracted toner amount (g)
[Charge amount under high temperature and high humidity]
Measurement was performed in the same manner as in the measurement of charge amount under normal temperature and normal humidity except that the measurement environment was set at a temperature of 45° C. and a relative humidity of 70%.

[Resin production]
[Production of polyester resin A]
Production Example A1 (Production of Resin A-1)
The inside of a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple was replaced with nitrogen, and 3253 g of propylene oxide (2.2) adduct of bisphenol A, 1003 g of terephthalic acid, di(2 - Ethylhexanoic acid) tin (II) 24 g and gallic acid 2.4 g are added, and the reaction system is heated to 235 ° C. while stirring under a nitrogen atmosphere, and after maintaining at 235 ° C. for 5 hours, The pressure was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160°C, and a mixture of 2,139 g of styrene, 535 g of stearyl methacrylate, 107 g of acrylic acid, and 321 g of dibutyl peroxide was added to the reaction system over 3 hours while maintaining the temperature at 160°C. Dripped. Thereafter, the reaction system was held at 160° C. for 30 minutes, then heated to 200° C., and the pressure in the flask was further lowered and held at 8 kPa for 1 hour. After returning to atmospheric pressure, the temperature was lowered to 190°C, 129 g of fumaric acid, 94 g of sebacic acid, 214 g of trimellitic anhydride, and 2.4 g of 4-tert-butylcatechol were added, and the temperature was increased to 210°C at 10°C/hr. After that, the reaction was carried out at 4 kPa to the desired softening point to obtain Resin A-1. Table 1 shows physical properties.

Production Example A2 (Production of Resin A-2)
Into a 20 L stainless steel kettle equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, raw material monomers for a polyester resin shown in Table 1, excluding trimellitic anhydride, were placed. After reacting at 230° C. for 8 hours in a nitrogen atmosphere, the mixture was reacted under reduced pressure of 1.3 kPa to 2.0 kPa for 4 hours. Furthermore, after adding trimellitic anhydride, the mixture was reacted at 180° C. for 3 hours to obtain an amorphous polyester resin A-2. Table 1 shows physical properties.

[Production of polyester resin B]
Production Example B1 (Production of Resin B-1)
Resin B-1 was obtained in the same manner as in Production Example A2, except that the raw material monomers for the polyester resin were changed as shown in Table 1. Table 1 shows physical properties.

[Production of composite resin D]
Production Example D1 (Production of Resin D-1)
The inside of a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple was purged with nitrogen, and 4313 g of propylene oxide (2.2) adduct of bisphenol A, 818 g of terephthalic acid, di(2 - Ethylhexanoic acid) tin (II) 30 g and gallic acid 3.0 g are added, and the reaction system is heated to 235 ° C. while stirring under a nitrogen atmosphere and maintained at 235 ° C. for 5 hours. The pressure was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture 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 to the reaction system over 3 hours while the temperature was kept at 160°C. Dripped. Thereafter, the reaction system was held at 160° C. for 30 minutes, then heated to 200° C., and the pressure in the flask was further lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, cool to 190 ° C., add 727 g of succinic acid, raise the temperature to 210 ° C. at 10 ° C./hr, and then react to the desired softening point at 4 kPa. -1 was obtained. Table 1 shows physical properties.

[Production of addition polymer E]
Production Example E1 (Synthesis of addition polymer E-1)
Raw material monomers of the types and amounts shown in Table 2 were mixed to prepare a monomer mixed solution with a total monomer amount of 100 g.
The inside of a four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, a stirrer, and a thermocouple is replaced with nitrogen, and 18 g of methyl ethyl ketone, 0.03 g of 2-mercaptoethanol, and 10% by mass of the monomer mixture are added, The temperature was raised to 75° C. while stirring. With the reaction system maintained at 75° C., the remaining 90% by mass of the monomer mixture, 0.27 g of 2-mercaptoethanol, 42 g of methyl ethyl ketone, and 2,2′-azobis(2,4-dimethylvaleronitrile) “V -65" (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 3 g of the mixture was added dropwise to the reaction system from the dropping funnel over 3 hours. After completion of the dropwise addition, the reaction system was kept at 75°C for 2 hours, then a solution of 3 g of V-65 dissolved in 5 g of methyl ethyl ketone was added, and the mixture was further kept at 75°C for 2 hours and at 80°C for 2 hours. Thereafter, methyl ethyl ketone was distilled off under reduced pressure to obtain addition polymer E-1. Table 2 shows the weight average molecular weight of the obtained addition polymer.

Production Examples E2 to E6 (synthesis of addition polymers E-2 to E-6)
Addition polymers E-2 to E-6 were obtained in the same manner as in Production Example E1, except that the raw material monomers were changed as shown in Table 2. Table 2 shows the weight average molecular weight.

[Production of crystalline polyester resin (C)]
Production Example C1 (Production of Resin C-1)
The interior of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple was replaced with nitrogen, the raw material monomers for the polyester resin shown in Table 3 were added, and the reaction system was stirred at 135 ° C. and maintained at 135° C. for 3 hours, then heated from 135° C. to 200° C. over 10 hours. After that, 23 g of di(2-ethylhexanoate) tin (II) was added to the reaction system, and the reaction system was further held at 200°C for 1 hour. A resin C-1, which is a crystalline polyester resin, was obtained. Table 3 shows physical properties.

[Production of aqueous dispersion of resin particles X]
Production Example X1 (Production of aqueous dispersion of resin particles X-1)
Resin A, Resin C, Addition Polymer E, and 100 g of methyl ethyl ketone shown in Table 4 were placed in a 2-liter container equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet tube, and heated at 73°C. It was allowed to dissolve for 2 hours. A 5% by mass sodium hydroxide aqueous solution was added to the resulting solution so that the degree of neutralization would be 60 mol % with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73° C. and stirring at 200 r/min, 100 g of deionized water was added over 50 minutes for phase inversion emulsification. The obtained solution was kept at 73° C., and methyl ethyl ketone was distilled off under reduced pressure to obtain a dispersion liquid. After that, the dispersion is cooled to 30° C. while stirring is continued, and deionized water is added so that the solid content concentration becomes 20% by mass, whereby resin A, resin C, and addition polymer E are mixed into the same particles. An aqueous dispersion of resin particles X-1 contained in was obtained. Table 4 shows physical properties.

Production Examples X2 to X8 (Production of aqueous dispersions of resin particles 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 resin was changed as shown in Table 4. Table 4 shows physical properties.

Production Example X9 (Production of aqueous dispersion of resin particles X-9)
A resin particle dispersion liquid X-9 was obtained in the same manner as in Production Example X1, except that the addition polymer E was not used. Table 4 shows physical properties.

Production Example Y1 (Production of Resin Particle Dispersion Y-1)
250 g of resin B-1 and 250 g of methyl ethyl ketone were placed in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, and 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 60 mol % with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73° C. and stirring at 200 r/min, 500 g of deionized water was added over 50 minutes for phase inversion emulsification. The obtained solution was kept at 73° C., and methyl ethyl ketone was distilled off under reduced pressure to obtain a dispersion liquid. Thereafter, the dispersion was cooled to 30° C. while stirring was continued, and then deionized water was added so that the solid content concentration was 20% by mass, thereby obtaining resin particle dispersion Y-1. The volume-median particle diameter _D50 of the resin particles in the resin particle dispersion liquid Y-1 was 0.04 μm, and the CV value was 29%.

Production Example S1 (Production of Resin Particle Dispersion S-1)
A resin particle dispersion liquid S-1 was obtained in the same manner as in Production Example Y1, except that the resin B-1 was changed to D-1. The volume median particle diameter _D50 of the resin particles in the resin particle dispersion liquid S-1 was 0.11 μm, and the CV value was 21%.

[Production of Release Agent Particle Dispersion]
Production Example W1 (Production of Release Agent Particle Dispersion W-1)
120 g of deionized water, 86 g of resin particle dispersion S-1, and 40 g of paraffin wax “HNP-9” (manufactured by Nippon Seiro Co., Ltd., melting point 75° C.) were added to a 1 L beaker, and the mixture was heated to 90 to 95° C. The mixture was melted while maintaining the temperature at 20° C. and stirred to obtain a molten mixture.
While maintaining the temperature of the resulting molten mixture at 90 to 95 ° C., after performing dispersion treatment for 20 minutes using an ultrasonic homogenizer "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.), room temperature (20 ° C.). cooled to Deionized water was added to the resulting dispersion to adjust the solid content concentration to 20% by mass to obtain release agent particle dispersion W-1. The release agent particles in the release agent particle dispersion W-1 had a volume median particle diameter _D50 of 0.47 μm and a CV value of 27%.

Production Example W2 (Production of Release Agent Particle Dispersion W-2)
Release agent particle dispersion W-2 was prepared in the same manner as in Production Example W1, except that the type of release agent was changed to Fischer-Tropsch wax "FNP-0090" (manufactured by Nippon Seiro Co., Ltd., melting point 90°C). Obtained. The release agent particles in the release agent particle dispersion W-2 had a volume median particle diameter _D50 of 0.45 μm and a CV value of 28%.

[Production of colorant particle dispersion]
Production Example Z1 (Production of Colorant Particle Dispersion Z-1)
In a 1 L beaker, copper phthalocyanine pigment "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd.) 100 g, polyoxyethylene (13) distyrenated phenyl ether "Emulgen A-60" (manufactured by Kao Corporation, nonionic interface Activator) 35 g and deionized water 300 g are mixed, and a homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used at room temperature (20 ° C.) at the rotation speed of the stirring blade. After dispersing at 8000 rpm for 1 hour, after 15 PASS treatment at a pressure of 150 MPa using "Microfluidizer M-110EH" (manufactured by Microfluidics), it is passed through a 200 mesh filter so that the solid content concentration is 20% by mass. Colorant particle dispersion Z-1 was obtained by adding deionized water. The volume-median particle size _D50 of the resulting colorant particles was 0.12 μm, and the CV value was 21%.

[Toner manufacturing]
Example 1 (Production of Toner 1)
500 g of an aqueous dispersion of resin particles X-1, 49 g of a release agent particle dispersion W-1, and a release agent particle dispersion were placed in a 3 L four-necked flask equipped with a dehydration tube, a stirrer, and a thermocouple. 49 g of W-2 and 63 g of colorant particle dispersion Z-1 were added and mixed at a temperature of 25.degree. Next, while stirring the mixture, an aqueous solution of 40 g of ammonium sulfate dissolved in 570 g of deionized water was added with a 4.8% by mass aqueous potassium hydroxide solution to adjust the pH to 8.2. After that, the temperature was raised to 58° C. over 2 hours and maintained at 58° C. until the volume-median particle size D ₅₀ of the aggregated particles reached 6.2 μm, to obtain a dispersion liquid of aggregated particles 1 . The obtained dispersion of Aggregated Particles 1 was cooled to 55° C., and while maintaining the temperature at 55° C., 48 g of Resin Particle Dispersion Y-1 was added to the dispersion of Aggregated Particles 1 over 90 minutes. A dispersion liquid of aggregated particles 2 in which resin particles were aggregated was obtained.
50 g of a naphthalenesulfonic acid formalin condensate sodium salt “Demoll MS” (manufactured by Kao Corporation, effective concentration: 20% by mass) and 1500 g of deionized water were added to the obtained dispersion of Aggregated Particles 2 . Thereafter, the temperature was raised to 75° C. over 1 hour and maintained at 75° C. until the circularity reached 0.970, thereby obtaining a dispersion liquid of fused particles in which aggregated particles were fused.
The obtained dispersion of fused particles 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 constant temperature vacuum dryer “DRV622DA” (manufactured by ADVANTEC) to obtain toner particles having a core-shell structure. Table 5 shows physical properties of the 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 physical properties of Toner 1 obtained.

[Evaluation of Toner]
The obtained Toner 1 was evaluated as follows.
[Evaluation of Image Density]
Using a printer "Microline (registered trademark) 5400" (manufactured by Oki Electric Industry Co., Ltd.) in which the fixing device is modified to have a variable temperature, the temperature of the fixing device is set to 130° C., and A4 sheets are printed in the vertical direction for 1.5 seconds. The toner was fixed on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.) at a high speed, and a printed matter was obtained in an environment of temperature 25° C. and humidity 50%.
Thirty sheets of high-quality paper "Excellent White Paper A4" (manufactured by Oki Electric Industry Co., Ltd.) were placed under the printed matter, and the reflected image density of the solid image portion of the output printed matter was measured using a colorimeter "SpectroEye" (manufactured by GretagMacbeth). Measurement was performed using light irradiation conditions: standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard), and the image density was obtained by averaging the values obtained by measuring arbitrary 10 points on the image. The higher the numerical value, the better the image density. Table 5 shows the evaluation results.

[Evaluation of Fog]
The toner is mounted on a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Electric Industry Co., Ltd.), and the high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.) ) was printed with a print density of 1%. After repeating this process and printing a total of 1,000 sheets, blank printing was performed, and the printer was stopped during the blank printing. The developing unit was taken out from the printer, and "Scotch (registered trademark) Mending Tape 810" (manufactured by 3M Japan Co., Ltd., width: 18 mm) was adhered on the photoreceptor, and the toner on the photoreceptor was peeled off with the tape.
The tape peeled off from the photoreceptor and the unused tape are pasted on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), and the tape peeled off from the photoreceptor and the unused tape are measured with a colorimeter "SpectroEye" (manufactured by GretagMacbeth, light irradiation conditions; standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard). The color difference (ΔE) between the tape peeled from the photoreceptor and the unused tape was defined as fog. The smaller the fog value, the better the image without fog. Table 5 shows the evaluation results.

Examples 2 to 8, Comparative Example 1 (manufacture of toners 2 to 9)
Toners 2 to 9 were obtained in the same manner as in Example 1, except that the aqueous dispersion of resin particles X-1 was changed to the aqueous dispersion of resin particles X shown in Table 5. Toners 2 to 9 were also evaluated in the same manner as in Example 1. Table 5 shows the evaluation results of toners 2 to 9.

Comparative Example 2 (Production of Toner 10)
500 g of an aqueous dispersion of resin particles X-9, 49 g of release agent particle dispersion W-1, and release agent particle dispersion W-2 were placed in a 3 L four-necked flask equipped with a stirrer and a thermocouple. 49 g of the colorant particle dispersion Z-1, 63 g of the colorant particle dispersion Z-1, and 25 g of a 10% by weight aqueous solution of polyoxyethylene (50) lauryl ether "Emulgen 150" (manufactured by Kao Corporation, nonionic surfactant) were added, and the temperature was adjusted to Mixed at 25°C. Toner 10 was obtained in the same manner as in Example 1 for subsequent operations. Toner 10 was also evaluated in the same manner as in Example 1. Table 5 shows the evaluation results of Toner 10.

As described above, according to the production method of the present invention, toner containing toner particles having a narrow particle size distribution can be obtained from the results of Examples and Comparative Examples. On the other hand, in the production method of Comparative Example 1, since the fine particles aggregated in the aggregation step did not contain the addition polymer E, coarse aggregated particles were generated, and the particle size distribution of the toner particles contained in the toner was considered to be broadened. . Further, the toner obtained by the production method of Comparative Example 1 had low chargeability, and caused fogging in image printing under a high-temperature and high-humidity environment.
Further, the toner obtained by the production method of the present invention does not expose the surfactant to the surface of the toner particles even after being stored in a high-temperature, high-humidity environment. Indicated. On the other hand, as shown in Comparative Example 2, the toner obtained by the manufacturing method using the surfactant in step 2 was stored in a high-temperature and high-humidity environment so that the surfactant was exposed to the surface of the toner particles. , it is considered that the chargeability became low. Since the toner obtained by the production method of the present invention exhibits high chargeability in a high-temperature and high-humidity environment, even in image printing in a high-temperature and high-humidity environment, a good image with a small fog value could be obtained. .
Furthermore, the toner obtained by the manufacturing method of the present invention was able to obtain a printed matter with a high image density.

Claims (7)

A method for producing a toner for developing an electrostatic charge image, comprising steps 1 to 3 below,
Step 1: Mix the polyester resin A and the addition polymer E to obtain an aqueous dispersion of resin particles X containing the polyester resin A and the addition polymer E Step 2: Resin particles X in an aqueous medium Aggregate to Obtain Aggregated Particles Step 3: Fusing the Aggregated Particles Obtained in Step 2 to Obtain Fused Particles The addition polymer E is an addition polymerizable monomer having a styrene compound and a polyalkylene oxide group. A method for producing a toner for electrostatic charge image development, which is an addition polymer of raw material monomers containing 2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein step 2 includes adhering resin particles Y containing a polyester-based resin B to said aggregated particles. 3. The method for producing a toner for electrostatic charge image development according to claim 1, wherein the raw material monomer of the addition polymer E further contains a styrene compound polymer having an addition polymerizable functional group at one end. 4. The method for producing a toner for electrostatic charge image development according to claim 1, wherein the content of the addition polymer E in the resin particles X is 1% by mass or more and 10% by mass or less. 5. The method for producing a toner for electrostatic charge image development according to claim 1, wherein the volume median particle diameter _D50 of the resin particles X is 0.05 μm or more and 0.5 μm or less. 6. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the resin particles X do not contain a coloring agent. 7. The method for producing a toner for electrostatic charge image development according to claim 1, wherein the amount of the surfactant used in step 2 is less than 5 parts by mass with respect to 100 parts by mass of the resin particles X.