JP2020173418A - Toner for electrostatic charge image development - Google Patents

Abstract

To provide a toner for electrostatic charge image development that exhibits excellent storage stability and excellent pigment dispersibility, and a method for manufacturing the toner.SOLUTION: There are included (1) a resin composition (A-P) that is obtained by condensing an amorphous polyester resin (A) having an acid radical and an amine compound, wherein the amorphous polyester resin (A) is a polycondensate of an alcohol component including an alkylene oxide adduct of bisphenol A and a carboxylic acid component including a monocarboxylic acid compound, (2) a toner for electrostatic charge image development that contains a coloring material, an addition polymer of a polymerizable monomer including a styrene compound, and a resin composition (A-P), wherein the resin composition (A-P) is a resin composition obtained by condensing an amorphous polyester resin (A) having an acid radical and an amine compound, and the amorphous polyester resin (A) is a polycondensate of an alcohol component including an alkylene oxide adduct of bisphenol A and a carboxylic acid component including a monocarboxylic acid compound, and (3) a method for manufacturing a toner for electrostatic charge image development that includes: a step 1 of dispersing a polymerizable monomer composition including a coloring material, a resin composition (A-P), and a polymerizable monomer including a styrene compound in an aqueous medium; and a step 2 of performing suspension polymerization of the polymerizable monomer composition in the aqueous medium, wherein the resin composition (A-P) is a resin composition obtained by condensing an amorphous polyester resin (A) having an acid radical and an amine compound, and the amorphous polyester resin (A) is a polycondensate of an alcohol component including an alkylene oxide adduct of bisphenol A and a carboxylic acid component including a monocarboxylic acid compound.SELECTED DRAWING: None

Description

The present invention relates to a resin composition used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc., a toner for developing an electrostatic charge image containing the resin composition, and the toner. Regarding the manufacturing method, etc.

In the field of electrophotographic, in order to reduce the environmental load, it is required to reduce the amount of adhesion of toner that is melted by heat and fixed on paper, that is, the amount of adhesion of toner is reduced. The problem of reducing the amount of adhesion is that it is difficult to obtain a high image density. Further, if the pigment dispersion is insufficient, high coloring power cannot be obtained, and even if the amount of pigment is increased, aggregation is more likely to occur, and the coloring power is limited. Therefore, it is known to use a pigment dispersant to improve the coloring power of the toner.
For example, Patent Document 1 describes a metal phthalocyanine or a metal phthalocyanine derivative in which the central metal can have a five-coordination structure or a six-coordination structure, and n that can be coordinated to the central metal of the metal phthalocyanine or the metal phthalocyanine derivative. -A pigment dispersant characterized by containing at least an electron-donating compound is described. According to the pigment dispersant, it is described that the pigment can be easily finely dispersed in the dispersion medium.
In addition, Patent Document 2 describes a polyallylamine derivative having a specific structure as providing a fine particle powder dispersible compound having excellent compatibility with a wide range of resins and having excellent pigment dispersibility. Further, Patent Document 3 describes a polyallylamine derivative as a pigment dispersant.

Japanese Unexamined Patent Publication No. 2003-277643 Japanese Unexamined Patent Publication No. 9-169821 JP-A-2017-203143

The dispersant described in Patent Document 1 is said to be able to finely disperse phthalocyanine pigments in toner particles, but the dispersant is used for pigments other than phthalocyanine (for example, quinacridone pigments and naphthol pigments). The pigment dispersibility was insufficient. Further, Patent Documents 2 and 3 also describe that carbon black and phthalocyanine pigments can be finely dispersed in a binder resin. However, since the toner obtained by adding the dispersant is plasticized, there arises a problem that the storage stability under high temperature and high humidity is deteriorated.
The present invention relates to a resin composition exhibiting excellent storage stability and excellent pigment dispersibility, a toner for developing an electrostatic charge image containing the resin composition, a method for producing the toner, and the like.

The present inventors have described above by providing the toner with a resin composition (AP) obtained by condensing a predetermined amorphous polyester resin (A) having an acid group and an amine compound. It has been found that the problems of storage stability and pigment dispersibility can be solved.

That is, the present invention relates to the following embodiments [1] to [3].
[1] A resin composition (AP) obtained by condensing an amorphous polyester resin (A) having an acid group and an amine compound.
A resin composition in which the amorphous polyester resin (A) is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing a monocarboxylic acid compound.
[2] A toner for developing an electrostatic charge image, which comprises a colorant, an addition polymer of a polymerizable monomer containing a styrene compound, and a resin composition (AP).
The resin composition (AP) is a resin composition obtained by condensing an amorphous polyester resin (A) having an acid group and an amine compound.
A toner for developing an electrostatic charge image, wherein the amorphous polyester resin (A) is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing a monocarboxylic acid compound.
[3] Step 1: A step of dispersing a polymerizable monomer composition containing a colorant, a resin composition (AP), and a polymerizable monomer containing a styrene-based compound in an aqueous medium, and a step of dispersing the polymerizable monomer composition in an aqueous medium. Step 2: Suspension polymerization of the polymerizable monomer composition in an aqueous medium.
The resin composition (AP) is a resin composition obtained by condensing an amorphous polyester resin (A) having an acid group and an amine compound.
Production of a toner for static charge image development, wherein the amorphous polyester resin (A) is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing a monocarboxylic acid compound. Method.

According to the present invention, it is possible to provide a resin composition exhibiting excellent storage stability and excellent pigment dispersibility, a toner for developing an electrostatic charge image containing the resin composition, a method for producing the toner, and the like. ..

[Toner for static charge image development]
The toner for developing an electrostatic charge image of the present invention (hereinafter, also simply referred to as “toner of the present invention”) is an addition polymer of a polymerizable monomer containing a colorant and a styrene compound (hereinafter, simply “additional weight”). It also contains "coalescence (B)") and a resin composition (AP) (hereinafter, also simply referred to as "resin composition (AP)").
The resin composition (AP) is a resin composition obtained by condensing an amorphous polyester resin (A) having an acid group (hereinafter, also simply referred to as "resin (A)") with an amine compound. Is.
The amorphous polyester resin (A) is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing a monocarboxylic acid compound.
According to the toner of the present invention, excellent storage stability and excellent pigment dispersibility in the toner are exhibited.

The reason why the effect of the present invention can be obtained is not clear, but it is considered as follows.
The resin composition (AP) contains a portion derived from an amine compound in its structure, and by acting as a dispersant for the colorant, the colorant is finely dispersed in the binder resin composition. Conceivable. Further, since it has a constituent component derived from a monocarboxylic acid compound, it is considered that the wettability with the colorant is improved and the reaggregation of the colorant is suppressed. Further, since the colorant is dispersed by the resin composition (AP), plasticization does not occur due to the addition of the dispersant, high storage stability can be obtained, and it is considered to be compatible with the above-mentioned high dispersibility.

Definitions of various terms in the present specification are shown below.
The crystallinity of a resin is represented by the ratio of the softening point to the maximum endothermic temperature by differential scanning calorimetry (DSC), i.e. the crystallinity index defined by "softening point / maximum endothermic temperature". Generally, when the crystallinity index exceeds 1.4, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous portions. In the present invention, the "crystalline resin" has a crystallinity index of 0.6 or more, preferably 0.7 or more, more preferably 0.9 or more, and 1.4 or less, preferably 1.2. The following resins are referred to, and the “amorphous resin” refers to a resin having a crystallinity index of more than 1.4 or less than 0.6.
The above-mentioned "maximum endothermic peak temperature" refers to the temperature of the peak having the largest peak area among the endothermic peaks observed under the conditions of the measurement method described in the examples.
The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, the production conditions (for example, reaction temperature, reaction time, cooling rate) and the like.
The "polyester resin" may contain a polyester resin modified to such an extent that its characteristics are not substantially impaired. Examples of the modified polyester resin include a urethane-modified polyester resin in which the polyester resin is modified by a urethane bond, an epoxy-modified polyester resin in which the polyester resin is modified by an epoxy bond, and a composite having a polyester component and an addition polymerization resin component. Resin is mentioned.
"Bisphenol A" means 2,2-bis (4-hydroxyphenyl) propane.
Examples of the "carboxylic acid compound" include carboxylic acids, their anhydrides, and alkyl esters having 1 or more and 3 or less carbon atoms.
"(Meta) acrylic acid" refers to acrylic acid or methacrylic acid. Further, with respect to the alkyl moiety, "(iso)" means normal alkyl or isoalkyl.
The “resin component of the toner” means a resin component contained in the toner including the addition polymer (B), the resin composition (AP), and the resin (C).

The toner of the present invention contains a colorant, an addition polymer (B), and a resin composition (AP).
The toner of the present invention contains, for example, toner particles and an external additive.
The toner particles preferably contain a colorant, an addition polymer (B), and a resin composition (AP).
Then, the toner particles may contain, for example, a colorant derivative, a mold release agent, a charge control agent, and other additives.

<Additional polymer (B)>
The toner of the present invention contains an addition polymer (B) of a polymerizable monomer containing a styrene compound.
The polymerizable monomer of the addition polymer (B) preferably contains a styrene compound and a (meth) acrylic acid ester.

Examples of the styrene-based compound include substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group or a salt thereof and the like.
Examples of styrene-based compounds include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. Be done. Of these, styrene is preferable.
The amount of the styrene-based compound is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 95% by mass or more in the polymerizable monomer. Is 90% by mass or less.

The (meth) acrylic acid ester is preferably a (meth) acrylic acid ester having an aliphatic hydrocarbon group.
The aliphatic hydrocarbon group of the (meth) acrylic acid ester having an aliphatic hydrocarbon group preferably has 1 or more carbon atoms, more preferably 2 or more, still more preferably 3 or more, still more preferably 4 or more, and It is preferably 22 or less, more preferably 18 or less, still more preferably 12 or less, still more preferably 8 or less, still more preferably 6 or less.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkynyl group, and an alkenyl group. Among these, an alkyl group and an alkenyl group are preferable, and an alkyl group is more preferable. The aliphatic hydrocarbon group may be either branched or linear.
Examples of the (meth) acrylic acid ester include (meth) acrylic acid (iso) propyl, (meth) acrylic acid (iso) butyl, (meth) acrylic acid (iso) hexyl, (meth) acrylic acid cyclohexyl, and (meth) acrylic acid ester. ) Acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl, (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, (meth) ) Acrylic acid (iso) behenyl can be mentioned. Of these, butyl (meth) acrylate is preferable.

The amount of the (meth) acrylic acid alkyl ester is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass, in the polymerizable monomer. Hereinafter, it is more preferably 30% by mass or less.

Examples of other polymerizable monomers include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; and vinyl esters such as vinyl acetate and vinyl propionate. (Meta) Acrylic acid aminoalkyl esters such as dimethylaminoethyl (meth) acrylic acid; Vinyl ethers such as methyl vinyl ether; Vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone. ..

The total amount of the styrene compound and the (meth) acrylic acid ester in the polymerizable monomer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100. It is not more than mass%, more preferably 100% by mass.
The addition polymer (B) can be obtained by the addition polymerization of the method described later.

<Resin composition (AP)>
The resin composition (AP) of the present invention is a resin composition obtained by condensing an amorphous polyester resin (A) having an acid group and an amine compound. As described above, in the resin composition (AP), for example, a reaction product of the resin (A) and the amine compound and a by-product derived from the amine compound, and an unreacted resin (A) and an unreacted product. Residual amine compounds and the like are included. Then, it is considered that the reaction product of the resin (A) and the amine compound and the by-product derived from the amine compound acts as a dispersant of the colorant in the resin composition (AP).

[Amorphous polyester resin (A)]
The amorphous polyester resin (A) has an acid group.
Examples of the acid group include a carboxy group and a sulfo group. Among these, a carboxy group is preferable.
Examples of the amorphous polyester resin (A) include an amorphous polyester resin, an amorphous composite resin having a polyester resin segment and a vinyl resin segment. Among these, an amorphous polyester resin is preferable.
The amorphous polyester resin is a polycondensate of an alcohol component and a carboxylic acid component, but the amorphous polyester resin of the present invention contains a monocarboxylic acid as a carboxylic acid component. The alcohol component and the carboxylic acid component contained in the amorphous polyester resin in the present invention will be described below.

(Alcohol component)
The alcohol component preferably contains at least one selected from the group consisting of an alkylene oxide adduct of bisphenol A (hereinafter, also referred to as "BPA-AO") and an aliphatic diol having 2 to 18 carbon atoms. More preferably, it contains BPA-AO. The BPA-AO preferably has the formula (I):

[In the formula, OR ¹¹ and R ¹² O are alkyleneoxy groups, and R ¹¹ and R ¹² are independently alkylene groups having 1 or more and 4 or less carbon atoms (preferably ethylene or propylene groups), and x. And y are the average number of moles of alkylene oxide added, each independently being a positive number, and the average value of the sum of x and y is preferably 1 or more, more preferably 1.5 or more, and It is preferably 16 or less, more preferably 8 or less, and even more preferably 4 or less. ], BPA-AO represented by.
BPA-AO is preferably a propylene oxide adduct of bisphenol A (hereinafter, also referred to as "BPA-PO"), an ethylene oxide adduct of bisphenol A (hereinafter, also referred to as "BPA-EO"), and more preferably BPA. -PO. These BPA-AOs may be used alone or in combination of two or more.
The amount of BPA-AO is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 98 mol% or more, and 100 mol% or less in the alcohol component. It is more preferably 100 mol%.

The alcohol component may contain another alcohol component different from BPA-AO. Examples of other alcohol components include linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols.

The linear or branched aliphatic diol preferably has 2 or more carbon atoms, and preferably 18 or less, more preferably 14 or less, still more preferably 10 or less, still more preferably 6 or less.
Examples of the linear or branched aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 2,3-Butanediol, Neopentyl glycol, 1,4-Butendiol, 1,2-Pentanediol, 1,4-Pentanediol, 2,4-Pentanediol, 1,5-Pentanediol, 1,2- -Hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 3,3-dimethyl-1,2-butanediol, 1,7-heptanediol, 1,8-octane Examples thereof include diols, 1,9-nonanediols, 1,10-decanediols, 1,11-undecanediols, 1,12-dodecanediols, 1,13-tridecanediols and 1,14-tetradecanediols.
Examples of the alicyclic diol include hydrogenated bisphenol A and alkylene oxide adducts of hydrogenated bisphenol A having 2 or more and 4 or less carbon atoms (average number of moles added 2 or more and 12 or less).
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sorbitol.
From the viewpoint of adjusting the molecular weight and softening point of the obtained polyester, the alcohol component may contain a monohydric alcohol.
As these alcohol components, one kind or two or more kinds may be used.

(Carboxylic acid component)
The carboxylic acid component in the present invention contains a monocarboxylic acid compound from the viewpoint of improving wettability with a colorant, and other carboxylic acids include, for example, a dicarboxylic acid compound and a trivalent or higher valent carboxylic acid. Examples include compounds.

Examples of the monocarboxylic acid compound include an aliphatic monocarboxylic acid compound, an aromatic monocarboxylic acid compound, and an alicyclic monocarboxylic acid compound, which are selected from the aliphatic monocarboxylic acid compound and the aromatic monocarboxylic acid compound. It is preferable that the amount is one or more, and an aliphatic monocarboxylic acid is more preferable.
The number of carbon atoms of the monocarboxylic acid compound is preferably 2 or more, more preferably 3 or more, still more preferably 6 or more, and preferably 30 or less, more preferably 20 or less.
Examples of the aliphatic monocarboxylic acid compound include octanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. Of these, stearic acid is preferred.
Examples of the aromatic monocarboxylic acid compound include benzoic acid.
Among these, stearic acid and benzoic acid are preferable, and stearic acid is more preferable.
The amount of the monocarboxylic acid compound is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 30 mol% or less, more preferably 30 mol% or more, in the carboxylic acid component. It is 20 mol% or less, more preferably 15 mol% or less.

Examples of the dicarboxylic acid compound include an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, and an alicyclic dicarboxylic acid compound.
The number of carbon atoms of the dicarboxylic acid compound is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
Aliphatic dicarboxylic acids include, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, pentandioic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, Examples thereof include succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The aliphatic hydrocarbon group preferably has 8 or more carbon atoms, more preferably 9 or more carbon atoms, and preferably 16 or less, more preferably 14 or less carbon atoms. The aliphatic hydrocarbon group may be either a straight chain or a branched chain, and may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Examples of the succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include octenyl succinic acid, nonenyl succinic acid, decenyl succinic acid, undecenyl succinic acid, dodecyl succinic acid, dodecenyl succinic acid, and tridecenyl succinic acid. , Tetradecenyl succinic acid, tetrapropenyl succinic acid.

Among these dicarboxylic acid compounds, aromatic dicarboxylic acid is preferable, and terephthalic acid is more preferable.
The amount of the aromatic dicarboxylic acid compound is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 65 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more in the carboxylic acid component. % Or more, preferably 99 mol% or less, more preferably 98 mol% or less, still more preferably 96 mol% or less.

Examples of the trivalent or higher valent carboxylic acid compound include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Among these, it is preferable to contain trimellitic acid or an anhydride thereof.
The content of the trivalent or higher polyvalent carboxylic acid is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 1 mol% or less, and 0 mol% or more in the carboxylic acid component. is there.
One kind or two or more kinds of these carboxylic acid components may be used.

The equivalent ratio [COOH group / OH group] of the carboxy group (COOH group) of the carboxylic acid component to the hydroxy group (OH group) of the alcohol component is preferably 0.7 or more, more preferably 0.8 or more, and It is preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 1.0 or less.

(Physical properties of resin (A))
The softening point of the resin (A) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 95 ° C. or higher, and the low-temperature fixability of the toner is improved from the viewpoint of further improving the storage stability of the toner. From the viewpoint of further improvement, the temperature is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower.

The glass transition temperature of the resin (A) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, further preferably 53 ° C. or higher, and the low temperature fixability of the toner from the viewpoint of further improving the storage stability of the toner. From the viewpoint of further improving the temperature, the temperature is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 70 ° C. or lower, still more preferably 60 ° C. or lower.

The acid value of the resin (A) is preferably 0.5 mgKOH / g from the viewpoint of facilitating the acquisition of the resin composition (AP) having excellent storage stability and pigment dispersibility, and from the viewpoint of interaction with the colorant. As described above, it is more preferably 1 mgKOH / g or more, further preferably 2 mgKOH / g or more, and preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, still more preferably 10 mgKOH / g or less.

The hydroxyl value of the resin (A) is preferably 2 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 30 mgKOH / g or more, and preferably 70 mgKOH / g or less, more preferably 60 mgKOH / g or less. More preferably, it is 50 mgKOH / g or less.

The number average molecular weight of the resin (A) is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 1,800 or more, and preferably 30,000 or less, more preferably 8,000 or more. Below, it is more preferably 4,000 or less.

The weight average molecular weight of the resin (A) is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, and preferably 100,000 or less, more preferably 50,000 or more. Below, it is more preferably 10,000 or less.

The softening point, glass transition temperature, acid value, hydroxyl value, number average molecular weight, and weight average molecular weight of the resin (A) depend on the type and ratio of the raw material monomer and the production conditions such as reaction temperature, reaction time, and cooling rate. It can be adjusted as appropriate. Those values are obtained by the method described in Examples described later. When two or more kinds of resins (A) are used in combination, it is preferable that the values of physical properties obtained as a mixture thereof are within the above ranges.

From the viewpoint of pigment dispersibility, the amount of water vapor adsorbed by the resin (A) is preferably 0.5 cm ³ / g or more, more preferably 1.0 cm ³ / g or more, and further preferably 1.5 cm ³ / g or more. , And preferably 7.0 cm ³ / g or less, more preferably 6.0 cm ³ / g or less, still more preferably 5.0 cm ³ / g or less.
The amount of water vapor adsorbed is measured by the method described in Examples.
The amount of water vapor adsorbed by the resin (A) indicates the degree of affinity of the resin (A) with water, and when the amount of water vapor adsorbed by the resin (A) is within the above range, the pigment dispersibility is further improved, which is preferable.

(Manufacturing method of resin (A))
The resin (A) may be produced, for example, by a method including a step a of performing a polycondensation reaction with an alcohol component and a carboxylic acid component.
In step a, if necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, or titanium diisopropoxybis (triethanolaminate) is added to the alcohol component and the carboxylic acid component. 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) of alcohol component and carboxylic acid component. Polycondensation may be performed using 0.001 part by mass or more and 0.5 part by mass or less with respect to 100 parts by mass of the total amount.
When a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation reaction, it is preferably 0.001 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component, if necessary. A radical polymerization inhibitor of 0.5 parts by mass or less may be used. Examples of the radical polymerization inhibitor include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, and preferably 260 ° C. or lower, more preferably 240 ° C. or lower. The polycondensation may be carried out in an inert gas atmosphere.

[Amine compound]
The amine compound is preferably a compound having an amino group (-NH ₂ , -NHR, -NRR'). Here, R and R'represent a hydrocarbon group having 1 or more and 5 or less carbon atoms. The amine compound is a compound that can be incorporated into the molecular skeleton of the resin (A) by undergoing a condensation reaction with the acid group of the resin (A).
The amine compound may contain a functional group other than the amino group. Examples of the functional group include a hydroxy group, a formyl group, an acetal group, an oxime group, and a thiol group.
The amount of the amine compound is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the resin (A), from the viewpoint of further improving storage stability and pigment dispersibility. It is more preferably 0.5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

Examples of the amine compound include polyalkyleneimine, polyallylamine, (poly) ethylenepolyamine, alkanolamine, and alkylamine.
Among these, polyalkyleneimine is preferable from the viewpoint of pigment dispersibility.

(Polyalkyleneimine)
The polyalkyleneimine is preferably a polyalkyleneimine having an alkylene group having 2 or more and 5 or less carbon atoms.
The polyalkyleneimine is preferably a polyalkyleneimine having an alkylene group having 2 or more and 4 or less carbon atoms, more preferably polyethyleneimine or polypropyleneimine, and further preferably polyethyleneimine. These may be used alone or in combination of two or more.

The number average molecular weight of the polyalkyleneimine is preferably 150 or more, more preferably 500 or more, still more preferably 800 or more, still more preferably 1,000 or more, and preferably 10,000 or less, more preferably 5, It is 000 or less, more preferably 4,000 or less.
The value of the molecular weight is obtained by the method described in Examples.

(Polyallylamine)
Examples of polyallylamine include homopolymers of allyl compounds such as allylamine and dimethylallylamine, and polymers having an amino group in the side chain such as copolymers.
The weight average molecular weight of polyallylamine is preferably 800 or more, more preferably 1,000 or more, still more preferably 1,500 or more, and preferably 10,000 or less, more preferably 5,000 or less, even more preferably. Is less than 4,000.

(Polyethylene polyamine)
Examples of the (poly) ethylene polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like. Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferable.

(Alkanolamine)
The alkanolamine is preferably an alkanolamine having 2 or more and 9 or less carbon atoms. Examples of the alkanolamine include primary alkanolamines such as monoethanolamine, monopropanolamine and monobutanolamine; monoalkanol secondary amines such as N-methylethanolamine and N-methylpropanolamine, diethanolamine and diisopropanolamine. Secondary alkanolamines such as dialkanol secondary amines; monoalkanol tertiary amines such as N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-diethylethanolamine, N-methyldiethanolamine, N Examples thereof include dialkanol tertiary amines such as ethyldiethanolamine, and tertiary alkanolamines such as trialkanol tertiary amines such as triethanolamine and triisopropanolamine. Among these, tertiary alkanolamines having 2 or more and 9 or less carbon atoms are preferable, and N, N-dimethylethanolamine is more preferable.

(Alkylamine)
The alkylamine is preferably an alkylamine having 1 or more and 6 or less carbon atoms. Examples of the alkylamine include primary amines such as propylamine, butylamine and hexylamine; and secondary amines such as diethylamine and dipropylamine.

As described above, the resin composition (AP) of the present invention is obtained by condensing an amorphous polyester resin (A) having an acid group with an amine compound.
The method for producing the resin composition (AP) is, for example,
Step A: A step of condensing an amorphous polyester resin (A) having an acid group with an amine compound to obtain a resin composition (AP).
including.

The temperature at the time of condensation in step A is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, further preferably 130 ° C. or higher, and preferably 235 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 170 ° C. It is below ° C.
The condensation of the resin (A) and the amine compound in the step A may be carried out under pressure or reduced pressure, but is preferably carried out under normal pressure from the viewpoint of ease of reaction.
The condensation time may be appropriately changed depending on the reaction temperature and the like, but is preferably 10 minutes or more, more preferably 30 minutes or more, further preferably 1 hour or more, and preferably 24 hours or less, more preferably. It is 12 hours or less, more preferably 6 hours or less.

The blending amount of the amine compound in the step A is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the resin (A) as described above from the viewpoint of improving the storage stability and the pigment dispersibility. It is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

The softening point of the resin composition (AP) is preferably 85 ° C. or higher, more preferably 95 ° C. or higher, still more preferably 100 ° C. or higher, and preferably 100 ° C. or higher, from the viewpoint of further improving the storage stability of the toner. It is 125 ° C. or lower, more preferably 115 ° C. or lower, and even more preferably 110 ° C. or lower.

The glass transition temperature of the resin composition (AP) is preferably 42 ° C. or higher, more preferably 52 ° C. or higher, still more preferably 55 ° C. or higher, and the toner, from the viewpoint of further improving the storage stability of the toner. From the viewpoint of further improving the low temperature fixability, the temperature is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, further preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.

Water vapor adsorption amount of the resin composition (A-P), from the viewpoint of pigment dispersibility, preferably 1.0 cm ³ / g or more, more preferably 2.0 cm ³ / g or more, more preferably 3.0 cm ³ / g or more, and, preferably 9.0 cm ³ / g or less, more preferably 7.5 cm ³ / g or less, further preferably 6.0 cm ³ / g or less.
The amount of water vapor adsorbed is measured by the method described in Examples.
The amount of water vapor adsorbed by the resin composition (AP) indicates the degree of affinity of the resin composition (AP) with water, and the amount of water vapor adsorbed by the resin composition (AP) is within the above range. This is preferable because the dispersibility of the pigment is further improved.

The content of the resin composition (AP) in the toner of the present invention is based on 100 parts by mass of the addition polymer (B) from the viewpoint of obtaining a toner exhibiting excellent storage stability and excellent pigment dispersibility. It is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass. Parts or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

<Crystalline polyester resin (C)>
The toner of the present invention may contain a crystalline polyester resin (C) (hereinafter, also simply referred to as "resin (C)") from the viewpoint of further improving low temperature fixability.
The crystalline polyester resin (C) is preferably a crystalline polyester resin having an acid group.
As the crystalline polyester resin (C), a crystalline composite resin having a crystalline polyester resin, a polyester resin segment, and a vinyl resin segment, which will be described later, is preferable. Among these, crystalline polyester is preferable.
The crystalline polyester resin is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
Hereinafter, the alcohol component and the carboxylic acid component of the crystalline polyester resin will be described.

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

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

The alcohol component may contain other alcohol components different from the α, ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α and ω-aliphatic diols, aromatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols.

The carboxylic acid component is preferably an aliphatic dicarboxylic acid. As the aliphatic dicarboxylic acid, a linear aliphatic dicarboxylic acid is preferable.
The aliphatic dicarboxylic acid has preferably 2 or more, more preferably 4 or more, and preferably 14 or less, more preferably 10 or less, still more preferably 8 or less.
Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Can be mentioned. Of these, fumaric acid is preferable.

The content of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 85 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% or less, and further. It is preferably 100 mol%.

In addition to the aliphatic dicarboxylic acid, the carboxylic acid component may contain an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a trivalent or higher polyvalent carboxylic acid.
Examples of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and trivalent or higher polyvalent carboxylic acids are the same as those exemplified above.
From the viewpoint of adjusting the molecular weight and softening point of the crystalline polyester resin, the carboxylic acid component may appropriately contain a monovalent carboxylic acid. These may be used alone or in combination of two or more.

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

(Physical properties of resin (C))
The softening point of the resin (C) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and the low temperature fixability of the toner is improved from the viewpoint of further improving the storage stability of the toner. From the viewpoint of further improvement, the temperature is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 115 ° C. or lower.

The melting point of the resin (C) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, and from the viewpoint of further improving the storage stability of the toner. From the viewpoint of further improving the low temperature fixability, the temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, and further preferably 120 ° C. or lower.

The acid value of the resin (C) is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less. More preferably, it is 20 mgKOH / g or less.

The hydroxyl value of the resin (C) is preferably 2 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 30 mgKOH / g or more, and preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g or less. , More preferably 45 mgKOH / g or less.

The number average molecular weight of the resin (C) is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 1,800 or more, and preferably 50,000 or less, more preferably 10,000 or more. Below, it is more preferably 8,000 or less.

The weight average molecular weight of the resin (C) is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, and preferably 100,000 or less, more preferably 80,000 or more. Below, it is more preferably 50,000 or less.

The softening point, melting point, acid value, hydroxyl value, number average molecular weight, and weight average molecular weight of the resin (C) are appropriately adjusted according to the type and ratio of the raw material monomers and the production conditions such as reaction temperature, reaction time, and cooling rate. can do. Those values are obtained by the method described in Examples described later. When two or more kinds of resins (C) are used in combination, it is preferable that the values of the softening point, the melting point, and the acid value obtained as a mixture thereof are within the above ranges.

The resin (C) can be obtained, for example, by polycondensing an alcohol component and a carboxylic acid component. The conditions for polycondensation are the same as those exemplified for the resin (A) described above.

The content of the resin (C) in the toner of the present invention is preferably 0 with respect to 100 parts by mass of the addition polymer (B) from the viewpoint of obtaining a toner exhibiting excellent storage stability and excellent low-temperature fixability. .3 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less. , More preferably 3 parts by mass or less.

The ratio [(AP) / (C)] of the resin composition (AP) to the resin (C) is preferably 30/70 or more, more preferably 50/50 or more, still more preferably 60/40. The above, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less.

The total content of the addition polymer (B), the resin composition (AP), and the resin (C) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 90% by mass or more, in the resin component of the toner. Is 95% by mass or more and 100% by mass or less.

<Colorant>
The colorant may be either a pigment or a dye.
Examples of pigments include azo pigments, phthalocyanine pigments, condensed polycyclic pigments, and lake pigments.
Examples of the azo pigment include C.I. I. Insoluble azo pigments such as Pigment Red 3, C.I. I. Pigment Red 48: 1 etc. Soluble Azo Pigment, C.I. I. Examples thereof include condensed azo pigments such as Pigment Red 144.
Examples of the phthalocyanine pigment include C.I. I. Pigment Blue 15: 3, copper phthalocyanine pigment, C.I. I. Examples thereof include polyhalogenated zinc phthalocyanine pigments such as Pigment Green 58.
Examples of the condensed polycyclic pigment include C.I. I. Anthraquinone pigments such as Pigment Red 177, C.I. I. Pigment Red 123 and other perylene pigments, C.I. I. Pigment Orange 43 and other perinone pigments, C.I. I. Pigment Red 122 and other quinacridone pigments, C.I. I. Pigment Red 269 and other naphthol pigments, C.I. I. Pigment Violet 23 and other dioxazine pigments, C.I. I. Pigment Yellow 139, 185 and other isoindolinone pigments, C.I. I. Isoindoline pigments such as Pigment Orange 66, C.I. I. Pigment Yellow 138 and other quinophthalone pigments, C.I. I. Pigment Yellow 150 and other nickel azo complex pigments, C.I. I. Pigment Red 88 and other indigo pigments, C.I. I. Pigment Green 8 and other metal complex pigments, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Examples thereof include diketopyrrolopyrrole pigments such as Pigment Orange 71.
Examples of the lake pigment include C.I. I. Pigment Red 57: 1.
Among these, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, naphthol pigments and lake pigments are preferable, and phthalocyanine pigments, quinacridone pigments and isoindolinone pigments are more preferable.
In the toner of the present invention, good pigment dispersibility can be obtained not only for phthalocyanine pigments but also for quinacridone pigments and naphthol pigments, which have conventionally been insufficient in pigment dispersibility. ing.

Examples of the dye include an azine dye, an anthraquinone dye, a perinone dye, and a rhodamine dye. More specifically, as a dye, for example, C.I. I. Solvent Black 5, C.I. I. Solvent Black 7, Spirit Black SB, Toluidine Blue, C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 59, C.I. I. Solvent Blue 74, 1-aminoanthraquinone, 2-aminoanthraquinone, hydroxyethylaminoanthraquinone, C.I. I. The hues of colorants such as Solvent Violet 47, Solvent Orange 60, Solvent Orange 78, Solvent Orange 90, Solvent Violet 29, Solvent Red 135, Solvent Red 162, Solvent Red 179, and Rhodamine-B Base are not particularly limited and are yellow. , Magenta, cyan, blue, red, orange, green and other chromatic pigments can be used. These may be used alone or in combination of two or more.

From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass with respect to 100 parts by mass of the total amount of the resin component of the toner. The above, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.

<Colorant derivative>
Examples of the colorant derivative include a colorant into which an acidic group or a basic group has been introduced or a salt thereof.
The colorant derivative is preferably a colorant having a sulfo group introduced therein or a salt thereof.
As a colorant, C.I. I. As the colorant derivative when Pigment Blue 15: 3 is used, a copper phthalocyanine compound having a sulfo group introduced therein or a salt thereof is preferable.
Examples of the salt include a halide salt, an amine salt, and a quaternary ammonium salt.
As the colorant derivative, a copper phthalocyanine derivative is preferable, and a sulfonate of copper phthalocyanine or a salt thereof is more preferable.
Examples of commercially available colorant derivatives include "5000S" and "22000" (all manufactured by Nippon Lubrizol Co., Ltd.) in the "SOLSPERSE" series.

The content of the colorant derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 1.5 parts by mass with respect to 100 parts by mass of the colorant from the viewpoint of improving the image density of the toner. It is 5 parts by mass or more, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less.

<Release agent>
The toner of the present invention may contain a mold release agent.
Examples of the release agent include polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax; hydrocarbon waxes such as microcrystallin wax, paraffin wax, Fishertropch wax, and sazole wax, or oxides thereof; carnauba wax. , Montan wax or ester waxes such as deoxidizing waxes and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like. These may be used alone or in combination of two or more.
The melting point of the release agent is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, further preferably 70 ° C. or higher, and preferably 130 ° C. or lower, more preferably 110 ° C. or lower, still more preferably 90 ° C. or lower. Is.

The content of the release agent is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 8 parts by mass or more, and preferably 30 parts by mass or more, based on 100 parts by mass of the total amount of the resin component of the toner. It is less than or equal to parts by mass, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less.

<Charge control agent>
The toner of the present invention may contain a charge control agent. The charge control agent may contain either a positive charge control agent or a negative charge control agent.
Positive charge control agents include niglosin dyes such as "niglosin base EX", "oil black BS", "oil black SO", "bontron (registered trademark) N-01", and "bontron (registered trademark) N-". 04 "," Bontron (registered trademark) N-07 "," Bontron (registered trademark) N-09 "," Bontron (registered trademark) N-11 "(all manufactured by Orient Chemical Industry Co., Ltd.), etc .; tertiary amine Triphenylmethane dye containing as a side chain, quaternary ammonium salt compound, for example, "Bontron (registered trademark) P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" ( Clariant Co., Ltd.), etc .; Polyamine resin, for example, "AFP-B" (manufactured by Orient Chemical Industry Co., Ltd.), etc .; Etc .; Examples thereof include styrene-acrylic resin, for example, "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.).

Examples of the negative charge control agent include metal-containing azo dyes such as "Varifast (registered trademark) Black 3804", "Bontron (registered trademark) S-31", "Bontron (registered trademark) S-32", and "Bontron". (Registered Trademark) S-34 "," Bontron (Registered Trademark) S-36 "(above, manufactured by Orient Chemical Industry Co., Ltd.)," Eisenspiron Black TRH "," T-77 "(Hodoya Chemical Industry Co., Ltd.) (Manufactured), etc .; Metal compounds of benzylic acid compounds, for example, "LR-147", "LR-297" (all manufactured by Nippon Carlit Co., Ltd.), etc .; Metal compounds of salicylic acid compounds, for example, "Bontron (registered trademark) E -81 "," Bontron (registered trademark) E-84 "," Bontron (registered trademark) E-88 "," Bontron E-304 "(all manufactured by Orient Chemical Industry Co., Ltd.)," TN-105 " Tsuchiya Chemical Industry Co., Ltd.); Copper phthalocyanine dye; quaternary ammonium salt, for example, "COPY CHARGE PX VP434" (manufactured by Clariant), nitroimidazole derivative, etc .; One or more of these charge control agents may be used.

The content of the charge control agent is preferably 0.01 part by mass or more, more preferably 0.2 part by mass or more, and further preferably 0.5 part by mass or more with respect to 100 parts by mass of the total amount of the resin component of the toner. And, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

<Other additives>
Toner particles include other additives such as magnetic powder, fluidity improver, conductivity modifier, reinforcing filler such as fibrous substance, antioxidant, antiaging agent, and cleaning property improver. It may be contained as appropriate.

The content of the toner particles in the toner 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, preferably 99.5% by mass or less. Is.

The volume median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm. It is as follows. In the present specification, the volume median particle size (D ₅₀ ) means a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.

<External agent>
The toner of the present invention may further contain an external additive in order to improve the fluidity. The external additive can be contained by treating the surface of the toner particles. Examples of the external additive include fine particles of inorganic materials such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as resin particles such as melamine-based resin fine particles and polytetrafluoroethylene resin fine particles. Be done. These may be used alone or in combination of two or more. Among these external additives, silica is preferable, and hydrophobic silica treated with a hydrophobizing agent is more preferable.

Examples of the hydrophobizing agent include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octylliethoxysilane (OTES), and methyltriethoxysilane. Of these, hexamethyldisilazane is preferable.

When the surface treatment of the toner particles is performed using an external additive, the content of the external additive is preferably 0.05 with respect to 100 parts by mass of the toner particles from the viewpoint of the chargeability and fluidity of the toner. By mass or more, more preferably 0.08 parts by mass or more, further preferably 0.1 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less. Is.

[Toner manufacturing method]
The toner of the present invention may be a toner obtained by any known method such as a melt-kneading method, an emulsification phase inversion method, a suspension polymerization method, an emulsion aggregation method, etc., but the productivity and dispersibility of the colorant From the viewpoint of the above, the suspension polymerization toner obtained by the suspension polymerization method is preferable.

In the case of a suspension polymerization toner, the method for producing the toner is, for example, Step 1: A polymerizable monomer containing a colorant, a resin composition (AP), and a polymerizable monomer containing a styrene compound. A step of dispersing the composition in an aqueous medium, and a step 2: a step of suspend-polymerizing the polymerizable monomer composition in an aqueous medium.
including.
The resin composition (AP) is a resin composition obtained by condensing an amorphous polyester resin (A) having an acid group with an amine compound.
Further, the resin (A) is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing a monocarboxylic acid compound.

<Step 1>
In step 1, for example, the following polymerizable monomer composition is dispersed in an aqueous medium.

[Polymerizable monomer composition]
The polymerizable monomer composition contains a colorant, a resin composition (AP), and a polymerizable monomer containing a styrene compound.
The polymerizable monomer composition includes, for example, a polymerization initiator, a charge control agent, a mold release agent, a magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, and aging. It may contain an inhibitor and a cleaning property improver. Further, the resin (C) may be contained.

The content of the polymerizable monomer is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, still more preferably 80% by mass or more in the polymerizable monomer composition. Yes, and preferably 95% by mass or less, more preferably 90% by mass or less.

The content of the colorant in the polymerizable monomer composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer. It is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less.

In the polymerizable monomer composition, the resin composition (AP) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 2 parts by mass or more, based on 100 parts by mass of the polymerizable monomer. Is 3 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.

When the resin (C) is contained, the resin (C) is preferably 0.5 parts by mass or more, more preferably 1 part by mass, based on 100 parts by mass of the polymerizable monomer in the polymerizable monomer composition. More than parts by mass, more preferably 1.5 parts by mass or more, still more preferably 2 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, further. It is preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

[Aqueous medium]
As the water-based medium, those containing water as a main component are preferable.
The content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 98% by mass or more, and 100% by mass or less. Yes, more preferably 100% by mass. As the water, deionized water or distilled water is preferable.
Examples of components other than water that can be contained in the aqueous medium include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and soluble in water such as cyclic ethers such as tetrahydrofuran. Organic solvent to be used.

[Polymerization initiator]
Examples of the polymerization initiator include azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) and peroxides such as dibutyl peroxide and dicumyl peroxide.
The content of the polymerization initiator is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 6 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is less than a part by mass.

In step 1, the method for dispersing the polymerizable composition is not particularly limited, but is preferably a step including the following steps 1-1 and 1-2.
Step 1-1: A step of mixing a colorant, a resin composition (AP), and a polymerizable monomer containing a styrene compound to obtain a polymerizable monomer composition. Step 1-2 : A step of putting the polymerizable monomer composition into an aqueous medium to obtain a suspension.

[Step 1-1]
In step 1-1, each component of the polymerizable monomer composition is heated and mixed.
Here, it is preferable to mix the charge control agent and the release agent.
The mixing temperature is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, still more preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.
It is preferable to add a polymerization initiator and mix after obtaining a polymerizable monomer composition in which each component is compatible.

[Step 1-2]
In step 1-2, the aqueous medium may be a mixed aqueous medium mixed with a dispersion stabilizer and a surfactant.
(Dispersion stabilizer)
Examples of the dispersion stabilizer include carbonates, metal phosphates, sulfates, and metal hydroxides. Examples of the carbonate include barium carbonate, calcium carbonate, and magnesium carbonate. Examples of the metal phosphate salt include aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate, and zinc phosphate. Examples of the sulfate include barium sulfate and calcium sulfate. Examples of the metal hydroxide include calcium hydroxide, aluminum hydroxide, magnesium hydroxide, and ferric hydroxide. Among these, calcium phosphate is preferable.
The amount of the dispersion stabilizer is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or more in the mixed aqueous medium. It is mass% or less, more preferably 10 mass% or less.

(Surfactant)
As the surfactant, various surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants can be used. Of these, anionic surfactants are preferred.
Examples of anionic surfactants include alkylbenzene sulfonates, alkyl sulfates, and polyoxyalkylene alkyl ether sulfates. As the salt, an alkali metal salt is preferable, and a sodium salt is more preferable.
Examples of the alkylbenzene sulfonate include sodium dodecylbenzenesulfonate. Examples of the alkyl sulfate include sodium dodecyl sulfate. The polyoxyalkylene alkyl ether sulfate is preferably a polyoxyethylene alkyl ether sulfate. Examples of the polyoxyalkylene alkyl ether sulfate include sodium polyoxyethylene lauryl ether sulfate. These may be used alone or in combination of two or more.
Among these, alkylbenzene sulfonate and polyoxyalkylene alkyl ether sulfate are preferable, dodecylbenzene sulfonate and polyoxyethylene lauryl ether sulfate are more preferable, and sodium dodecylbenzene sulfonate is further preferable.
The amount of the surfactant is preferably 1 mass ppm or more, more preferably 3 mass ppm or more, further preferably 5 mass ppm or more, and preferably 30 mass ppm or less, more preferably 20 mass ppm or more in the mixed aqueous medium. It is mass ppm or less, more preferably 10 mass ppm or less.

In step 1-2, the temperature at which the polymerizable monomer composition is put into the aqueous medium is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, still more preferably 50 ° C. or higher, and preferably It is 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.

It is preferable to stir and mix at the time of charging.
As the device used in this step, for example, it can be performed in a vertical stirring tank equipped with a stirring machine having a high shearing force. Commercially available products of agitators with high shearing force include, for example, "High Share Mixer" (manufactured by IKA), "TK Homomixer", and "TK Fillmix" (manufactured by Primix Corporation). ), Claremix (manufactured by M Technique Co., Ltd.).
The stirring speed is preferably 1,000 r / min or more, more preferably 5,000 r / min or more, further preferably 8,000 r / min or more, and preferably 30,000 r / min or less, more preferably 20. It is 000 r / min or less, more preferably 15,000 r / min or less.

The mass ratio of the polymerizable monomer composition to be charged to the aqueous medium (polymerizable monomer composition / aqueous medium) is preferably 3/97 or more, more preferably 5/95 or more, still more preferably 10 /. It is 90 or more, and preferably 40/60 or less, more preferably 30/70 or less, still more preferably 20/80 or less.

<Process 2>
In step 2, the polymerizable monomer is polymerized in the suspension.
The polymerization temperature is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, further preferably 60 ° C. or higher, and preferably 90 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 75 ° C. or lower. ..
The polymerization is preferably carried out with stirring. The device to be used is not particularly limited.
The stirring speed is preferably 50 r / min or more, more preferably 100 r / min or more, still more preferably 150 r / min or more, and preferably 1,000 r / min or less, more preferably 500 r / min or less, still more preferably. Is 300 r / min or less.

After the polymerization, it is preferable to add a mineral acid from the viewpoint of dissolving the dispersion stabilizer and facilitating the separation of the toner particles.
Examples of the mineral acid include hydrochloric acid and sulfuric acid.
After the polymerization, it is preferable to obtain toner particles by solid-liquid separation. After solid-liquid separation, it may be washed and dried. Examples of the drying method include a vacuum low temperature drying method, a vibration type fluid drying method, a spray drying method, a freeze drying method, and a flash jet method.

The method for producing toner may further include a step of mixing the obtained toner particles with an external additive.
The toner of the present invention is used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. In addition, the toner can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

Each property of the raw material, etc. was measured and evaluated by the following method.

[Measurement]
[Acid value and hydroxyl value of resin and resin composition]
The acid value and hydroxyl value of the resin were measured based on the method of JIS K0070: 1992. However, only the measurement solvent is a mixed solvent of ethanol and ether specified in JIS K0070: 1992, and in the case of an amorphous polyester resin and resin composition, a mixed solvent of acetone and toluene [acetone: toluene = 1: 1 (volume ratio)). ], In the case of crystalline polyester resin, it was changed to chloroform.

[Number average molecular weight and weight average molecular weight of resin and resin composition]
The molecular weight distribution was measured by the gel permeation chromatography (GPC) method obtained by the following method, and the number average molecular weight and the weight average molecular weight were determined.
(1) Preparation of sample solution Dissolve the sample in tetrahydrofuran (in the case of amorphous polyester resin) or chloroform (in the case of crystalline polyester resin) at 25 ° C. so that the concentration becomes 0.5 g / 100 mL. It was. Next, this solution was filtered using a fluororesin filter "DISMIC-25JP" (manufactured by ADVANTEC) having a pore size of 0.2 μm to remove insoluble matter, and used as a sample solution.
(2) Molecular weight measurement Using the following measuring device and analysis column, tetrahydrofuran (amorphous polyester resin) or chloroform (crystalline polyester resin) is flowed as an eluent at a flow rate of 1 mL per minute, and a constant temperature bath at 40 ° C. The column was stabilized inside. 100 μL of the sample solution was injected therein and the measurement was performed. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve of the several kinds of monodisperse polystyrene "A-500" (5.0 × ¹⁰ 2), "A-1000" (1.01 × ¹⁰ 3), "A-2500" (2.63 × 10 ³ ), “A-5000” (5.97 × 10 ³ ), “F-1” (1.02 × 10 ³ ), “F-2” (1.81 × 10 ⁴ ), “F-” 4 ”(3.97 × 10 ⁴ ),“ F-10 ”(9.64 × 10 ⁴ ),“ F-20 ”(1.90 × 10 ⁵ ),“ F-40 ”(4.27 × 10) ⁵ ), "F-80" (7.06 × 10 ⁵ ), “F-128” (1.09 × 10 ⁶ ) (all manufactured by Tosoh Corporation) were used as standard samples.
Measuring device: "HLC-8220CPC" (manufactured by Tosoh Corporation)
Analytical column: "GMHXL" + "G3000HXL" (manufactured by Tosoh Corporation)

[Softening point of resin and resin composition]
Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, and the diameter was 1 mm and the length was 1 mm. Extruded from the nozzle of. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was used as the softening point.

[Maximum peak temperature of endothermic reaction]
Using a differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.), a sample cooled from room temperature (20 ° C) to 0 ° C at a temperature lowering rate of 10 ° C / min was cooled to 0 ° C at the same temperature for 1 minute. After that, the measurement was carried out while raising the temperature to 180 ° C. at a heating rate of 10 ° C./min. The temperature of the largest endothermic peak among the observed endothermic peaks was defined as the maximum endothermic peak temperature.

[Glass transition temperature of amorphous polyester resin and resin composition]
Using a differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and then use the sample. The temperature was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the temperature of the sample is raised at a temperature rise rate of 10 ° C./min, and the temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent line indicating the maximum slope from the rising portion of the peak to the peak is set. The glass transition temperature was used.

[Amorphous polyester resin and water vapor adsorption amount of resin composition]
The amount of water vapor adsorption (cm ³ / g) at an equilibrium relative pressure of 0.85 to 0.90 was measured using a gas adsorption measuring device. Specific measurement conditions are shown below.
Measuring instrument: Multi-sample high-performance specific surface area / pore distribution measuring device 3Flex-3MP (manufactured by Micromeritics)
Dispersed adsorbent: Ion-exchanged water Pretreatment: 40 ° C for 4 hours or more Equilibrium relative pressure: 0.04 to 0.90 [0.04 to 0.10 (every 0.01), 0.10 to 0.90 (0) .25)]
Equilibrium interval: 20 seconds Measurement temperature: 30 ° C

[Melting point of crystalline polyester resin]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample into an aluminum pan, and cool down from room temperature to 10 ° C./min. The temperature was maintained at −10 ° C. for 1 minute. Next, the sample was heated to 200 ° C. at a heating rate of 10 ° C./min and cooled from that temperature to −30 ° C. at a temperature lowering rate of 10 ° C./min. Next, the temperature of the sample was raised at a heating rate of 10 ° C./min, and the peak temperature on the highest temperature side among the observed endothermic peaks was defined as the melting point.

[Number average molecular weight of polyalkyleneimine (Mn)]
The molecular weight distribution was measured by the gel permeation chromatography (GPC) method shown below, and the number average molecular weight was determined.
(1) Preparation of sample solution Polyalkyleneimine was dissolved in a solution prepared by dissolving Na ₂ SO ₄ in a 1 mass% acetic acid aqueous solution at 0.15 mol / L so that the concentration was 0.2 g / 100 mL. .. Next, this solution was filtered using a fluororesin filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 0.2 μm to remove insoluble components, and used as a sample solution.
(2) Molecular weight measurement Using the following measuring device and analytical column, a solution of Na ₂ SO ₄ dissolved in a 1% by mass acetic acid aqueous solution at 0.15 mol / L as an eluent was flowed at a flow rate of 1 mL per minute. The column was stabilized in a constant temperature bath at 40 ° C. 100 μL of the sample solution was injected therein and the measurement was performed. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. At this time, the calibration curve includes several types of standard pullulans "P-5" (5.9 x 10 ³ ), "P-50" (4.73 x 10 ⁴ ), and "P-200" (2.12 x). 10 ^5), was used to create "P-800" a (7.08 × ¹⁰ 5) (all manufactured by Showa Denko Co., Ltd.) as a standard sample.
Measuring device: "HLC-8320GPC" (manufactured by Tosoh Corporation)
Analytical column: α + α-M + α-M (manufactured by Tosoh Corporation)

[Melting point of mold release agent]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of a sample into an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from 200 ° C. It was cooled to 0 ° C. at a speed of 10 ° C./min. Next, the temperature of the sample was raised at a heating rate of 10 ° C./min, and the amount of heat was measured. The maximum peak temperature of the obtained endothermic reaction was taken as the melting point.

[Volume medium particle size of toner particles (D ₅₀ )]
The volume median particle diameter (D ₅₀ ) of the toner particles was measured as follows.
-Measuring device: "Coulter Multi-Sizar (registered trademark) III" (manufactured by Beckman Coulter Co., Ltd.)
・ Aperture diameter: 50 μm
-Analysis software: "Coulter Multi-Sizar (registered trademark) III version 3.51" (manufactured by Beckman Coulter Co., Ltd.)
-Electrolytic solution: "Isoton (registered trademark) II" (manufactured by Beckman Coulter Co., Ltd.)
-Dispersion: "Emulgen (registered trademark) 109P" [polyoxyethylene lauryl ether, manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance, Griffin method) = 13.6] is dissolved in the electrolytic solution to a concentration of 5 mass. % Dispersion was obtained.
-Dispersion condition: 10 mg of the measurement sample was added to 5 mL of the dispersion, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution was added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
-Measurement conditions: In a beaker, the sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. Then, the volume median particle size (D ₅₀ ) was determined from the obtained particle size distribution.

[Manufacturing of amorphous polyester resin]
Production Examples 1-1 to 1-4 (Production of resins AX-1, AX-2, A-1, A-2)
10 liters of alcohol component, carboxylic acid component, esterification catalyst, and esterification auxiliary catalyst shown in Table 1 equipped with a thermometer, a stainless steel stirring rod, a fractional distillation tower, a dehydration tube, a cooling tube, and a nitrogen introduction tube. It was placed in a four-necked flask, heated to 235 ° C. in a mantle heater in a nitrogen atmosphere, and reacted at normal pressure for 7 hours. Then, a reduced pressure reaction was carried out at 235 ° C. and 8 kPa to a desired acid value and softening point to obtain resins AX-1, AX-2, A-1, and A-2 which are amorphous polyester resins. Various physical properties were measured and shown in Table 1.

[Manufacturing of crystalline polyester resin]
Production Example 2 [Production of Resin C-1]
The alcohol component, carboxylic acid component, esterification catalyst, and polymerization inhibitor shown in Table 2 are equipped with a thermometer, a stainless steel stirring rod, a fractional distillation tower, a dehydration tube, a cooling tube, and a nitrogen introduction tube. The temperature was raised to 140 ° C. in a mantle heater in a nitrogen atmosphere, and the reaction was carried out for 5 hours, and then the temperature was gradually raised to 200 ° C. at a rate of 10 ° C./h. Then, the reaction was carried out at 8 kPa to a desired softening point to obtain resin C-1, which is a crystalline polyester resin. Various physical properties were measured and shown in Table 2.

[Manufacturing of resin composition (AP)]
Production Examples 3-1 and 3-2 [Production of resin compositions AP-1 and AP-2]
The amorphous polyester resin and polyalkyleneimine shown in Table 3 are placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a fractional distillation tower, a dehydration tube, a cooling tube, and a nitrogen introduction tube. The temperature was raised to 150 ° C. in a mantle heater in a nitrogen atmosphere, and the reaction was carried out at normal pressure for 3 hours to obtain resin compositions AP-1 and AP-2.

[Manufacturing of toner]
Examples 1 to 4 and Comparative Examples 1 to 4 (toners 1 to 4, 51 to 54)
<Preparation of dispersion>
In a 250 mL container, a total of the polymerizable monomer, resin, and colorant "Cyanine Blue 4927" (manufactured by Dainichiseika Kogyo Co., Ltd., CI Pigment Blue 15: 3) shown in Table 4 220 g of 110 g and 0.3 mm glass beads were charged and dispersed with a paint shaker for 0.5 hours to obtain a dispersion liquid.

<Preparation of resin solution>
100 g of the above dispersion is put into a 300 mL glass beaker, 1 g of the charge control agent "Bontron E-88" (manufactured by Orient Chemical Industry Co., Ltd., aluminum salicylate) and the release agent "HNP-9" (Nippon Seiwa). Paraffin wax manufactured by Co., Ltd., melting point: 75.5 ° C.) 10 g was added, and then the temperature was raised to 60 ° C. while stirring and mixing to uniformly dissolve. Then, 4 g of the polymerization initiator "V-65" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2,2'-azobis (2,4-dimethylvaleronitrile)) was added to prepare a resin solution.

<Preparation of aqueous medium>
In a 1 L glass beaker, 150 g of ion-exchanged water and tricalcium phosphate (chemical formula: 3 [Ca ₃ (PO ₄ ) ₂ ], Ca (OH) ₂ ) 10 mass% slurry "TCP-10, U" (Taipei Chemical Industry Co., Ltd.) 500 g (manufactured by Kao Co., Ltd.) was added, 0.004 g of anionic surfactant "Neoperex G-15" (manufactured by Kao Co., Ltd., sodium dodecylbenzene sulfonate) was added, and then stirred and mixed to prepare an aqueous medium. ..

<Suspension preparation>
Heat the above aqueous medium to 60 ° C in a 1 L glass beaker, add the above resin solution at once while maintaining 60 ° C, and use the homomixer "MARK II 2.5 type" (manufactured by Primix Corporation). , Stirred at 12,000 r / min for 4 minutes to obtain a suspension.

<Suspension polymerization>
The above suspension was transferred to a separable flask and polymerized at 70 ° C. and 200 r / min for 8 hours with stirring. Then, the temperature was raised to 80 ° C., and the residual monomer was distilled off under reduced pressure. The mixture was cooled to 20 ° C. while continuing stirring, and hydrochloric acid was added until the pH in the system became 1 or less. Next, the toner particles were sufficiently washed with ion-exchanged water and then dried to obtain toner particles having a volume median particle diameter (D ₅₀ ) of 6 μm.
To 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm) was added as an external additive, and 3600 r / with a Henschel mixer. By mixing for min and 5 minutes, an external additive treatment was performed to obtain toners 1-4, 51-54.

Examples 5 and 6, Comparative Examples 5 and 6 (Toner 5, 6, 55, 56)
<Preparation of dispersion>
In a 250 mL container, the polymerizable monomer, resin, colorant "Cyanine Blue 4927" (manufactured by Dainichiseika Kogyo Co., Ltd., CI Pigment Blue 15: 3) and coloring shown in Table 4 are used. A total of 110 g of the agent derivative "SOLPERSE 5000S" (manufactured by Nippon Lubrizol Co., Ltd., phthalocyanine derivative) and 220 g of 0.3 mm glass beads were added and dispersed with a paint shaker for 0.5 hours to obtain a dispersion liquid.

<Preparation of resin solution>
A resin solution was prepared in the same manner as in the preparation of the resin solution of Example 1 except that 100 g of the above dispersion was charged into a 300 mL glass beaker.
<Preparation of aqueous medium>
An aqueous medium was prepared in the same manner as in the preparation of the aqueous medium of Example 1.

<Suspension preparation>
A suspension was obtained from the above resin solution and an aqueous medium in the same manner as in the preparation of the suspension of Example 1.
<Suspension polymerization>
In the same manner as in <suspension polymerization> of Example 1, toner particles having a volume median particle diameter (D ₅₀ ) of 6 μm were obtained from the above suspension. Further, an external additive treatment was performed to obtain toners 5, 6, 55 and 56.

Examples 7, 8 and Comparative Examples 7, 8 (Toner 7, 8, 57, 58)
<Preparation of dispersion>
In a 250 mL container, a total of 110 g and 0.3 mm of the polymerizable monomer, resin, and colorant "Pariotol Yellow D1155" (manufactured by BASF, CI Pigment Yellow 185) shown in Table 4 220 g of the glass beads of No. 1 was charged and dispersed with a paint shaker for 0.5 hours to obtain a dispersion liquid.

<Preparation of resin solution>
A resin solution was prepared in the same manner as in the preparation of the resin solution of Example 1 except that 100 g of the above dispersion was charged into a 300 mL glass beaker.
<Preparation of aqueous medium>
An aqueous medium was prepared in the same manner as in the preparation of the aqueous medium of Example 1.

<Suspension preparation>
A suspension was obtained from the above resin solution and an aqueous medium in the same manner as in the preparation of the suspension of Example 1.
<Suspension polymerization>
In the same manner as in <suspension polymerization> of Example 1, toner particles having a volume median particle diameter (D ₅₀ ) of 6 μm were obtained from the above suspension. Further, the toner was treated with an external additive to obtain toners 7, 8, 57 and 58.

[Toner evaluation]
[Preservation]
4 g of toner was placed in a 20 mL container (diameter of about 3 cm) and left for 48 hours in an environment of a temperature of 55 ° C. and a relative humidity of 60%. Then, the degree of toner aggregation was visually observed every 6 hours for up to 72 hours. The larger the time value at the time when the occurrence of agglomeration is observed, the better the storage stability under high temperature and high humidity. The results are shown in Table 4. In Table 4, ">72" indicates that no aggregation was observed even after 72 hours.

[Pigment dispersibility]
0.1 g of toner was weighed in a 20 mL container (diameter of about 3 cm) so that the toner concentration was 1% by mass, and diluted with chloroform until a total of 10 g was obtained. Next, after sealing the container with a cap, the mixture was stirred and mixed with a test tube mixer (manufactured by AS ONE Corporation) to dissolve and disperse the toner in chloroform. The obtained sample was placed in a quartz cuvette cell (four-sided transmission) up to 10 mm or more from the bottom surface of the cell, and set in a nanoparticle analyzer "SZ-100" (manufactured by HORIBA, Ltd.). After inputting the refractive index of the sample and the refractive index and viscosity of the dispersion medium (chloroform), select the measurement mode (standard mode), calculation conditions (standard) and distribution form (other dispersion, standard), and in the toner at 25 ° C. The pigment particle size (nm) of was measured. The smaller the pigment particle size, the better the pigment dispersibility in the toner.

As shown in Table 4, it can be seen that the toner of the example is excellent in pigment dispersibility as compared with the toner of the comparative example while maintaining good storage stability.

Claims (9)

A resin composition (AP) obtained by condensing an amorphous polyester resin (A) having an acid group and an amine compound.
A resin composition in which the amorphous polyester resin (A) is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing a monocarboxylic acid compound. A toner for developing an electrostatic charge image, which contains a colorant, an addition polymer of a polymerizable monomer containing a styrene compound, and a resin composition (AP).
The resin composition (AP) is a resin composition obtained by condensing an amorphous polyester resin (A) having an acid group and an amine compound.
A toner for developing an electrostatic charge image, wherein the amorphous polyester resin (A) is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing a monocarboxylic acid compound. The toner for developing an electrostatic charge image according to claim 2, wherein the content of the resin composition (AP) is 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the addition polymer. The toner for static charge image development according to claim 2 or 3, wherein the monocarboxylic acid compound is at least one selected from an aliphatic monocarboxylic acid compound and an aromatic monocarboxylic acid compound. The toner for developing an electrostatic charge image according to any one of claims 2 to 4, wherein the alkylene oxide adduct of bisphenol A is a compound represented by the following formula (I).

[In the formula, OR ¹¹ and R ¹² O are alkyleneoxy groups, R ¹¹ and R ¹² are independently ethylene or propylene groups, and x and y indicate the average number of moles of alkylene oxide added, respectively. It is a positive number, and the value of the sum of x and y is 1 or more and 16 or less. ] The toner for developing an electrostatic charge image according to any one of claims 2 to 5, wherein the amine compound is a polyalkyleneimine having an alkylene group having 2 or more and 5 or less carbon atoms. The toner for developing an electrostatic charge image according to any one of claims 2 to 6, further containing a colorant derivative. The toner for developing an electrostatic charge image according to claim 7, wherein the colorant derivative is a copper phthalocyanine derivative. Step 1: Dispersing the polymerizable monomer composition containing the colorant, the resin composition (AP), and the polymerizable monomer containing the styrene-based compound in the aqueous medium, and Step 2: The step of suspend-polymerizing the polymerizable monomer composition in an aqueous medium is included.
The resin composition (AP) is a resin composition obtained by condensing an amorphous polyester resin (A) having an acid group and an amine compound.
Production of a toner for static charge image development, wherein the amorphous polyester resin (A) is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing a monocarboxylic acid compound. Method.