JP2019174672A - Toner for electrostatic charge image development - Google Patents

Abstract

To provide a toner for electrostatic charge image development excellent in durability and coloring power, and a method for manufacturing a toner for electrostatic charge image development.SOLUTION: (1) A toner for electrostatic charge image development contains an amorphous resin having an acidic group, a colorant, a wax, and a compound B having an aliphatic hydrocarbon group having 12 to 30 carbon atoms, and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group. (2) A method for manufacturing a toner for electrostatic charge image development includes a step of performing heat treatment under coexistence of an amorphous resin having an acidic group, a colorant, a wax, and a compound B having an aliphatic hydrocarbon group having 12 to 30 carbon atoms, and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group, wherein the highest temperature in the step of performing the heat treatment is equal to or higher than a temperature lower by 10°C than the melting point of the compound B and is equal to or lower than a temperature higher by 100°C than the melting point of the compound B.SELECTED DRAWING: None

Description

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

  In the field of electrophotography, with development of an electrophotographic system, development of toner for electrophotography corresponding to high image quality and high speed is demanded.

Patent Document 1 describes an electrostatic charge image developing toner having toner particles and an external additive externally added to the surface of the toner particles, and further having a nitrogen atomic weight fraction of 5% or more and 50% or less. It describes that the surface of the toner particles has an organic compound and that the organic compound is polyethyleneimine. It is described that the toner does not easily cause a decrease in image density and in-plane unevenness of an image without generating fog even in a high temperature and high humidity environment.
In Patent Document 2, an electrostatic charge image containing a binder resin and having toner particles having at least one compound selected from alkylated polyalkylene biguanides, alkylated polyalkylene guanidines, and alkylated polyalkyleneimines on the surface. A developing toner is described. Thus, it is described that a toner for developing an electrostatic charge image that suppresses occurrence of unevenness in image density can be obtained.

JP 2014-134681 A JP-A-2015-184474

From the viewpoint of reducing the environmental load, there is a demand for a toner exhibiting excellent coloring power that can obtain a higher image density even if the amount of toner used is small. Also, in the electrophotographic printing process, toner particles may collide with the developing roller due to causes such as the collapse of toner particles, and unevenness may occur, and the durability of the toner is required so that no unevenness occurs during printing.
The present invention relates to an electrostatic charge image developing toner excellent in durability and coloring power, and a method for producing the electrostatic charge image developing toner.

The present inventors have at least one basic group selected from the group consisting of an aliphatic hydrocarbon group having 12 to 30 carbon atoms, an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group. It has been found that by using Compound B having a nitrogen-containing group together with an amorphous resin having an acidic group, a colorant and a wax, an electrostatic charge image developing toner having excellent durability and coloring power can be obtained.
The present invention relates to the following [1] and [2].
[1] An amorphous resin having an acidic group, a colorant, a wax, an aliphatic hydrocarbon group having 12 to 30 carbon atoms, an amino group, an imino group, a cyano group, an azo group, a diazo group, and A toner for developing electrostatic images, comprising: Compound B having at least one basic nitrogen-containing group selected from the group consisting of an azide group.
[2] An amorphous resin having an acidic group, a colorant, a wax, an aliphatic hydrocarbon group having 12 to 30 carbon atoms, an amino group, an imino group, a cyano group, an azo group, a diazo group, and Including a step of heat treatment in the presence of compound B having at least one basic nitrogen-containing group selected from the group consisting of azide groups,
A method for producing a toner for developing an electrostatic charge image, wherein a maximum temperature in the heat treatment step is not less than a temperature 10 ° C. lower than the melting point of the compound B and not more than 100 ° C. higher than the melting point of the compound B.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the toner for electrostatic image development which is excellent in durability and coloring power, and the toner for electrostatic image development can be provided.

[Toner for electrostatic image development]
The toner for developing an electrostatic charge image of the present invention (hereinafter also simply referred to as “toner”) includes an amorphous resin having an acidic group (hereinafter also referred to as “amorphous resin A”), a colorant, a wax, , An aliphatic hydrocarbon group having 12 to 30 carbon atoms, and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an adi group Compound B (hereinafter also simply referred to as “Compound B”).
The toner of the present invention is excellent in durability and coloring power. The reason is not clear, but it can be considered as follows.

  In the present invention, an aliphatic hydrocarbon group having 12 or more and 30 or less carbon atoms, an amino group, an imino group, a cyano group, an azo group, and the like in a toner containing an amorphous resin A having an acidic group, a colorant, and a wax. And a compound B having at least one basic nitrogen-containing group selected from the group consisting of a group, a diazo group, and an azide group. Due to the acid-base interaction between the acidic group of the amorphous resin A and the basic nitrogen-containing group of the compound B, a toner in which the compound B is finely dispersed in the amorphous resin A is obtained. Along with this, a state is formed in which the aliphatic hydrocarbon group chemically bonded to the compound B is finely dispersed in the binder resin. The relatively hydrophobic coloring agent and wax are finely dispersed by the aliphatic hydrocarbon group, and the aliphatic hydrocarbon group acts as a nucleating agent on crystallization, so that the coloring agent and wax are finely dispersed. It exists stably. As a result, it is considered that a toner having excellent durability and coloring power can be obtained.

Definitions of various terms and the like in this specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio between the softening point of the resin and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement methods described in the examples described later. The crystalline resin is one having a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is one having a crystallinity index of less than 0.6 or greater than 1.4. The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate.
In this specification, the “binder resin” means a resin component contained in the toner containing the amorphous resin A.
In the specification, the carboxylic acid component of the polyester includes not only the compound but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of each carboxylic acid (an alkyl group having 1 to 3 carbon atoms). included.

<Amorphous resin A>
Amorphous resin A has an acidic group from the viewpoint of obtaining a toner excellent in durability and coloring power.
Examples of the acidic group include a carboxy group.
The amorphous resin A is not particularly limited as long as it has an acidic group, and examples thereof include an amorphous polyester resin. In the case of an amorphous polyester resin, the carboxy group at the end of the polymer chain of the resin corresponds to at least the aforementioned acidic group.
Examples of the amorphous polyester resin include an amorphous polyester resin and a modified amorphous polyester resin. Examples of the modified amorphous polyester resin include, for example, a urethane-modified polyester resin obtained by modifying an amorphous polyester resin with a urethane bond, an epoxy-modified polyester resin obtained by modifying an amorphous polyester resin with an epoxy bond, An amorphous composite resin containing a polyester resin segment and a vinyl resin segment can be mentioned.

The amorphous polyester resin is, for example, a condensate of an alcohol component and a carboxylic acid component.
Hereinafter, each component of the amorphous polyester resin will be described.
Examples of the alcohol component include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, aromatic diols are preferable.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(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 are the average number of moles of alkylene oxide added, And the value of the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less) alkylene of bisphenol A It is an oxide adduct.
Examples of the alkylene oxide adduct of bisphenol A include a polyoxypropylene adduct of bisphenol A [2,2-bis (4-hydroxyphenyl) propane] and a polyoxyethylene adduct of bisphenol A. These may use 1 type (s) or 2 or more types.
The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less in the alcohol component. More preferably, it is 100 mol%.

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

Examples of the carboxylic acid component include dicarboxylic acids and trivalent or higher polyvalent carboxylic acids.
Examples of the dicarboxylic acid include aromatic dicarboxylic acid, linear or branched aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. Among these, at least one selected from the group consisting of aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferable.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The amount of the aromatic dicarboxylic acid 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 90 mol% or less, more preferably It is 80 mol% or less, More preferably, it is 75 mol% or less.

The carbon number of 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.
Examples of linear or branched aliphatic dicarboxylic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid And succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Among these, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is preferable, and dodecenyl succinic acid is more preferable.
The amount of the linear or branched aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, and preferably 30 mol% in the carboxylic acid component. Hereinafter, it is more preferably 20 mol% or less, and still more preferably 10 mol% or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid.
In the case of containing a trivalent or higher polyvalent carboxylic acid, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% in the carboxylic acid component. More preferably, it is 20 mol% or more, and preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less.
These carboxylic acid components may be used alone or in combination of two or more.

  The ratio of the carboxyl 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, more preferably Is 1.2 or less.

[Method for producing amorphous resin A]
The amorphous resin A is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
If necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamate is added to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less; 0% of an esterification cocatalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) is 100 parts by mass with respect to 100 parts by mass of the alcohol component and the carboxylic acid component. Polycondensation may be performed using 0.001 part by mass or more and 0.5 part by mass or less.
The temperature of the polycondensation reaction is preferably 120 ° C or higher, more preferably 160 ° C or higher, still more preferably 180 ° C or higher, and preferably 250 ° C or lower, more preferably 230 ° C or lower. The polycondensation may be performed in an inert gas atmosphere.

[Physical properties of amorphous resin A]
The softening point of the amorphous resin A is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, from the viewpoint of further improving the heat-resistant storage stability, and further improves the low-temperature fixability. From the viewpoint of making it, it is preferably 140 ° C. or lower, more preferably 130 ° C. or lower, and still more preferably 125 ° C. or lower.

  The glass transition temperature of the amorphous resin A is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, and still more preferably 40 ° C. or higher, from the viewpoint of further improving the heat resistant storage stability. From the viewpoint of improving, it is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, and further preferably 70 ° C. or lower.

The acid value of the amorphous resin A is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, from the viewpoint of further improving the heat resistant storage stability and low-temperature fixability. , Preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, and still more preferably 30 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous resin A can be appropriately adjusted depending on the type of raw material monomer and the amount used, and the production conditions such as reaction temperature, reaction time, and cooling rate. These values are determined by the method described in the examples.
In addition, when using 2 or more types of amorphous resin A in combination, it is preferable that the value of the softening point, glass transition temperature, and acid value which were obtained as those mixtures is in the above-mentioned range, respectively.

In the toner binder resin, the content of the amorphous resin A is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 98% by mass or less. More preferably, it is 95 mass% or less, More preferably, it is 93 mass% or less.
The content of the amorphous resin A in the toner particles is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 98% by mass or less, more preferably Is 95% by mass or less, more preferably 93% by mass or less.

<Wax>
The toner contains a wax from the viewpoint of obtaining a toner having excellent durability and coloring power.
Examples of the wax include hydrocarbon wax, ester wax, silicone wax, fatty acid amide wax, fatty acids, higher alcohols, and fatty acid metal salts.
Examples of the hydrocarbon wax include mineral hydrocarbons such as paraffin wax, and synthetic hydrocarbon waxes such as polyolefin waxes such as polyethylene wax, polypropylene wax, polybutene wax, and Fischer-Tropsch wax.
Examples of the ester wax include minerals such as montan wax or petroleum ester wax; plant ester waxes such as carnauba wax, rice wax, and candelilla wax; and animal ester waxes such as beeswax.
Examples of the fatty acid amide wax include oleic acid amide and stearic acid amide.
These may use 1 type (s) or 2 or more types.
Among these, from the viewpoint of further improving durability and coloring power, hydrocarbon waxes and ester waxes are preferable, hydrocarbon waxes are more preferable, synthetic hydrocarbon waxes are more preferable, and Fischer-Tropsch waxes are further preferable.

The melting point of the wax is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 85 ° C. or higher, more preferably 95 ° C. or higher, more preferably 100 ° C. or higher, from the viewpoint of further improving durability and coloring power. And preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and still more preferably 140 ° C. or lower.
The content of the wax is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of further improving durability and coloring power. And preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

<Colorant>
The toner contains a colorant from the viewpoint of obtaining a toner having excellent durability and coloring power.
As the colorant, pigments and dyes are used, and pigments are preferable from the viewpoint of improving the coloring power of the toner. As the pigment, both inorganic pigments and organic pigments can be used, but organic pigments are preferred.
Examples of inorganic pigments include carbon black and inorganic composite oxides.
Examples of organic pigments include magenta pigments, cyan pigments, and yellow pigments.
Examples of magenta organic pigments include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds, and more. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19. Of these, naphthol compounds are preferred, and C.I. I. Pigment Red 269 is more preferable.

  Examples of cyan organic pigments include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. Among these, a copper phthalocyanine compound is preferable, and C.I. I. Pigment Blue 15: 3 is more preferable.

Examples of yellow organic pigments include azo compounds such as monoazo compounds, disazo compounds, and condensed azo compounds, isoindolinone compounds, isoindoline compounds, benzimidazolone compounds, anthraquinone compounds, azo metal complexes, and methine compounds. More specifically, C.I. I. Pigment yellow 17, 74, 93, 95, 109, 111, 128, 139, 151, 154, 155, 174, 180, 185. Among these, azo compounds are preferable, monoazo compounds and disazo compounds are more preferable. I. Pigment Yellow 74 and 180 are more preferable, and C.I. I. Pigment Yellow 180 is more preferable.
Examples of the dye include acridine dyes, azo dyes, benzoquinone dyes, azine dyes, anthraquinone dyes, indigo dyes, phthalocyanine dyes, and aniline black dyes.
These colorants may be used alone or in combination of two or more.

The content of the colorant is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 9 parts by mass or more with respect to 100 parts by mass of the resin component of the toner from the viewpoint of improving the coloring power of the toner. And preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.
From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more in the toner particles, and preferably It is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

<Compound B>
Compound B has an aliphatic hydrocarbon group having 12 to 30 carbon atoms and a basic nitrogen-containing group from the viewpoint of obtaining a toner having excellent durability and coloring power. Compound B is preferably dispersed in the amorphous resin. That is, it is preferable that the compound B is dispersed inside the toner particles.

Basic nitrogen-containing groups include amino groups, imino groups (═NH), cyano groups (—CN), azo groups (—N═N—), diazo groups (═N ₂ ), and azido groups (—N ₃ ). Is at least one selected from the group consisting of
The amino group may be a primary amino group, a secondary amino group, or a tertiary amino group.
From the viewpoint of the affinity of Compound B for amorphous resin A, an amino group is preferred.

  Examples of the functional group other than the basic nitrogen-containing group include a hydroxy group, a formyl group, an acetal group, an oxime group, and a thiol group.

Compound B has an aliphatic hydrocarbon group having 12 to 30 carbon atoms from the viewpoint of obtaining a toner having excellent durability and coloring power.
The number of carbon atoms of the aliphatic hydrocarbon group is preferably 14 or more, more preferably 16 or more, still more preferably 20 or more, and preferably 24 or less, from the viewpoint of further improving the durability and coloring power of the toner. More preferably, it is 22 or less.
The aliphatic hydrocarbon group may be branched or linear, but is preferably linear.
Examples of the aliphatic hydrocarbon group include dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, and docosyl group. Among these, from the viewpoint of further improving the durability and coloring power of the toner, an octadecyl group and a docosyl group are preferable, and a docosyl group is more preferable.

Compound B is, for example, a reaction product of a basic nitrogen-containing group material and an aliphatic hydrocarbon group material.
Examples of the basic nitrogen-containing group raw material include polyalkyleneimine, polyallylamine, and polyaminoalkyl methacrylate.
Examples of the polyalkyleneimine include polyethyleneimine.
Examples of the polyaminoalkyl methacrylate include polydimethylaminoethyl methacrylate.
Among these, polyethyleneimine is preferable.
The polyethyleneimine preferably contains a primary amino group, a secondary amino group, and a tertiary amino group and has a branched structure.
Examples of the commercially available polyethyleneimine include “SP-003”, “SP-006”, “SP-012”, and “SP-018” (manufactured by Junsei Chemical Co., Ltd.) of the “Epomin” series. .

  The number average molecular weight of the basic nitrogen-containing group raw material is preferably 100 or more, more preferably 500 or more, still more preferably 1,000 or more, and preferably from the viewpoint of adsorptivity to the resin having an acidic group. 15,000 or less, More preferably, it is 10,000 or less, More preferably, it is 5,000 or less.

Examples of the aliphatic hydrocarbon group raw material include aliphatic hydrocarbon compounds having a reactive functional group and having 12 to 30 carbon atoms. Examples of the reactive functional group include a carboxy group, a halogeno group, an epoxy group, a formyl group, and an isocyanate group. Examples of the halogeno group include a chloro group, a bromo group, and an iodo group. Among these, from the viewpoints of safety and reactivity, a carboxy group and a halogeno group are preferable, and a halogeno group is more preferable.
Examples of the aliphatic hydrocarbon compound having a reactive functional group include halogenated alkanes and aliphatic monocarboxylic acids. Of these, halogenated alkanes are preferred.
Examples of the halogenated alkane include 1-chlorododecane, 1-bromododecane, 1-chlorotetradecane, 1-bromotetradecane, 1-chlorohexadecane, 1-bromohexadecane, 1-chlorooctadecane, 1-bromooctadecane, 1- Examples include chloroicosane, 1-bromoicosane, 1-chlorodocosane, and 1-bromodocosane.

  The content of the halogenated alkane in the aliphatic hydrocarbon group raw material is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, from the viewpoint of obtaining a toner having excellent durability and coloring power. And it is 100 mass% or less, More preferably, it is 100 mass%.

[Method for Producing Compound B]
Compound B is obtained by a reaction between a basic nitrogen-containing group material and an aliphatic hydrocarbon group material. When acid is generated during the reaction, a neutralizing agent may be used. Examples of the neutralizing agent include basic compounds, alkali metal salts are preferable, and potassium carbonate, sodium carbonate, and cesium carbonate are more preferable.
The reaction temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower.

The ratio (A / N) of the reactive functional group (A) of the aliphatic hydrocarbon group material to the basic nitrogen-containing group (N) of the basic nitrogen-containing group material is preferably 0.2 or more, more preferably It is 0.3 or more, more preferably 0.4 or more, and preferably 0.7 or less, more preferably 0.6 or less, and still more preferably 0.5 or less.
The ratio (A / N) is calculated as follows.
Ratio (A / N) = [number of reactive functional groups per molecule of aliphatic hydrocarbon group raw material (A) × (charge amount of aliphatic hydrocarbon group raw material / molecular weight of aliphatic hydrocarbon group raw material)] / [base Amine value of basic nitrogen-containing group raw material (mmol / g) x amount of basic nitrogen-containing group raw material]
However, in the polyolefin skeleton raw material having a maleic anhydride moiety, the number of reactive functional groups per molecule is 1.
The amine value of the basic nitrogen-containing group material can be measured by hydrochloric acid titration method or perchloric acid titration.

[Physical properties of compound B]
The melting point of Compound B is preferably 34 ° C. or higher, more preferably 45 ° C. or higher, further preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of further improving the durability and coloring power of the toner. The temperature is preferably 150 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 80 ° C. or lower.

  The number average molecular weight of the compound B is preferably 500 or more, more preferably 800 or more, still more preferably 1,000 or more, and preferably 10,000 from the viewpoint of further improving the durability and coloring power of the toner. Hereinafter, more preferably 7,000 or less, and still more preferably 5,000 or less.

The amine value of Compound B is preferably 1 mmol / g or more, more preferably 3 mmol / g or more, still more preferably 5 mmol / g or more, and preferably from the viewpoint of further improving the durability and coloring power of the toner. 50 mmol / g or less, more preferably 30 mmol / g or less, still more preferably 15 mmol / g or less.
The amine value of Compound B can be measured by the method described above.

  The content of the compound B is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts from the viewpoint of further improving the durability and coloring power of the toner with respect to 100 parts by mass of the binder resin. It is at least 30 parts by mass, more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass, even more preferably at most 6 parts by mass.

The content of the compound B is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably from the viewpoint of further improving the durability and coloring power of the toner with respect to 100 parts by mass of the amorphous resin A. It is 3 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, and further preferably 6 parts by mass or less.
The content of the compound B is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 30% by mass or less, from the viewpoint of further improving the durability and coloring power of the toner in the toner particles. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 6 mass% or less.

<Charge control agent>
The toner may contain a charge control agent.
The charge control agent may contain either a positive charge control agent or a negative charge control agent.
Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-04”, “Bontron N-07”. ”,“ Bontron N-09 ”,“ Bontron N-11 ”(manufactured by Orient Chemical Co., Ltd.) and the like; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as“ Bontron P-51 "(manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; polyamine resin such as" AFP-B "(manufactured by Orient Chemical Industry Co., Ltd.), etc. Imidazole derivatives such as “PLZ-2001”, “PLZ-800”; "(Above, manufactured by Shikoku Chemicals Corporation) and the like; styrene - acrylic resin, for example," FCA-701PT "(manufactured by Fujikura Kasei), and the like.

Examples of the negatively chargeable charge control agent include metal-containing azo dyes such as “Varifirst Black 3804”, “Bontron S-31”, “Bontron S-32”, “Bontron S-34”, “Bontron S-36” ( As described above, manufactured by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH”, “T-77” (manufactured by Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds such as “LR-147”, “ LR-297 "(manufactured by Nippon Carlit Co., Ltd.), etc .; metal compounds of salicylic acid compounds such as" Bontron E-81 "," Bontron E-84 "," Bontron E-88 "," Bontron E-304 " (Above, made by Orient Chemical Co., Ltd.), “TN-105” (made by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dye; quaternary ammonium salt For example, “COPY CHARGE NX VP434” (manufactured by Clariant), nitroimidazole derivatives, etc .; organometallic compounds, etc. may be mentioned.
Among charge control agents, negatively chargeable charge control agents are preferable, and metal compounds of salicylic acid compounds are more preferable.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 100 parts by mass of the binder resin. Is 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less.

  In addition, the toner may contain additives such as magnetic powder, fluidity improver, conductivity adjuster, reinforcing filler such as fibrous substance, antioxidant, anti-aging agent, and cleanability improver.

The toner includes, for example, toner particles. The toner particles preferably contain an amorphous resin A, a colorant, a wax, and a compound B. The charge control agent and other additives are preferably contained in the toner particles.
Although the toner particles can be used as the toner as they are, it is preferable to use a toner obtained by adding an external additive described later to the surface of the toner particles.
The toner is preferably used as a dry toner.

[Toner Production Method]
The toner may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, an emulsion polymerization method, or an emulsion aggregation method, but from the viewpoint of productivity and dispersibility of the colorant. Therefore, a pulverized toner obtained by melt kneading is preferable.
The toner production method of the present invention preferably includes an amorphous resin A having an acidic group, a colorant, a wax, an aliphatic hydrocarbon group having 12 to 30 carbon atoms, an amino group, an imino group, A step of heat treatment in the presence of compound B having at least one basic nitrogen-containing group selected from the group consisting of a cyano group, an azo group, a diazo group, and an azide group.
Here, the maximum temperature of the heat treatment step is not less than a temperature 10 ° C. lower than the melting point of the compound B and not more than 100 ° C. higher than the melting point of the compound B.
With such a manufacturing method, the durability and coloring power of the toner can be further improved. Although it is not certain, the amorphous resin A and the compound B exert a chemical interaction by heat treatment at a temperature lower than the melting point of the compound B by 10 ° C. or more in the coexistence of the amorphous resin A and the compound B. However, the compound B is not completely compatible, and the compound B can be finely dispersed in the binder resin. The aliphatic hydrocarbon group of the compound B improves the dispersibility of the colorant and the wax, and is durable and colored. It is considered that a toner having excellent strength can be obtained.

The heat treatment step is a treatment step at the highest temperature in the presence of the amorphous resin A and the compound B in the toner production process.
For example, in the melt-kneading method, the melt-kneading process described later corresponds to the heat treatment process. In the emulsion aggregation method, the fusion step after aggregation corresponds to the heat treatment step.

  From the viewpoint of further improving the durability and coloring power of the toner, the maximum temperature of the heat treatment step is preferably at least 10 ° C lower than the melting point of Compound B, more preferably at least 5 ° C lower than the melting point of Compound B, and more Preferably at a temperature higher than the melting point of Compound B, more preferably at a temperature higher than 5 ° C. above the melting point of Compound B, more preferably at a temperature higher than 10 ° C. above the melting point of Compound B, more preferably at a temperature higher than 15 ° C. above the melting point of Compound B. Yes, and preferably 100 ° C. or higher than the melting point of Compound B, more preferably 60 ° C. or lower than the melting point of Compound B, more preferably 30 ° C. or lower than the melting point of Compound B.

In the case of a pulverized toner, the toner production method was obtained, for example, in Step 1: Step of melt-kneading a mixture containing amorphous resin A, a colorant, wax, and Compound B, and Step 2: Step 1. And crushing and classifying the melt-kneaded product to obtain toner particles.
It is preferable that the maximum temperature in the said process 1 is the range of the maximum temperature of the process to heat-treat.

In step 1, an additive such as a charge control agent may be included in the mixture. These toner materials are preferably mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to the kneader.
The melt kneading in Step 1 can be performed using a known kneader such as a closed kneader, a single screw extruder, a twin screw extruder, or an open roll kneader. Among these, a twin screw extruder capable of setting the kneading temperature widely is preferable.
The temperature for melt kneading is preferably 80 ° C. or higher and 160 ° C. or lower.
The melt-kneaded product obtained in step 1 is cooled to such an extent that it can be crushed, and then subjected to subsequent step 2.

The pulverization in step 2 may be performed in multiple stages. For example, the melt-kneaded material may be coarsely pulverized to 1 mm or more and 5 mm or less, and further pulverized to a desired particle size.
Examples of the pulverizer suitably used for coarse pulverization include a hammer mill, an atomizer, and a rotoxplex. Examples of the pulverizer suitably used for fine pulverization include a fluidized bed jet mill, a collision plate jet mill, and a rotary mechanical mill. Among these, from the viewpoint of grinding efficiency, a fluidized bed jet mill and a collision plate jet mill are preferable, and a collision plate jet mill is more preferable.

  Examples of the classifier used for classification include a rotor classifier, an airflow classifier, an inertia classifier, and a sieve classifier. In the classification step, the pulverized product that has been removed due to insufficient pulverization may be subjected to the pulverization step again, and the pulverization step and the classification step may be repeated as necessary.

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 10 μm or less, from the viewpoint of obtaining a high-quality image. Preferably it is 8 micrometers or less.
The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, still more preferably 16% or more, and preferably 45% or less, more preferably 40%, from the viewpoint of obtaining a high-quality image. % Or less.

The toner is preferably added to the surface of the toner particles using a fluidizing agent or the like as an external additive.
Examples of the external additive include inorganic fine particles such as hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable.
When the external additive is used, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the toner particles. The amount is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and still more preferably 4 parts by mass or less.

  The toner is used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method or the like. The toner can be used as a one-component developer or a two-component developer mixed with a carrier.

  Each property value was measured and evaluated by the following method.

[Measurement]
[Acid value of the resin]
The acid value of the resin was measured according to the neutralization titration method described in JIS K 0070-1992. However, the measurement solvent was chloroform.

[Softening point, crystallinity index, melting point and glass transition temperature of resin]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a length of 1 mm and a length of 1 mm. 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 taken as the softening point.
(2) Crystallinity Index Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample is weighed into an aluminum pan, and the temperature lowering rate from room temperature (20 ° C.) is 10 ° C. / Cooled to 0 ° C. in min. Next, the sample was kept as it was for 1 minute, and then the temperature was raised to 180 ° C. at a temperature rising rate of 10 ° C./min, and the amount of heat was measured. Of the observed endothermic peaks, the temperature of the peak with the largest peak area is defined as the maximum endothermic peak temperature (1), and (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)), The 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 a sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature Then, it was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the sample was heated at a temperature rising rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic 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 the peak is observed, the temperature of the peak is measured, and when the step is observed without the peak being observed, the tangent indicating the maximum slope of the curve of the step and the step The temperature at the intersection with the extension of the base line on the low temperature side was defined as the glass transition temperature.

[Melting point of wax and compound B]
Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and then cooled down from 200 ° C. to 10 ° C./min. At 0 ° C. Next, the sample was heated at a temperature rising rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[Number average molecular weight of basic nitrogen-containing base material]
The number average molecular weight was determined by the gel permeation chromatography (GPC) method shown below.
(1) Preparation of sample solution The raw material is dissolved in a 1 mass% acetic acid aqueous solution containing 0.15 mol / L Na ₂ SO ₄ so that the sample concentration is 0.2 g / 100 mL. Subsequently, 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 to obtain a sample solution.
(2) Molecular weight measurement Using the following measuring apparatus and analytical column, a 1 mass% acetic acid aqueous solution containing 0.15 mol / L Na ₂ SO ₄ as an eluent was flowed at a flow rate of 1 mL / min, and a constant temperature of 40 ° C. Stabilize the column in the bath. 100 μL of the sample solution was injected therein and the molecular weight was measured. The molecular weight (number average molecular weight Mn) of the sample is several standard pullulans (type name (Mw): “P-5” (5.9 × 10 ³ ), “P-50” (4.73 × 10 ⁴ ), “P-200” (2.12 × 10 ⁵ ), “P-800” (7.08 × 10 ⁵ ); all manufactured by Showa Denko KK) were used as standard samples and calculated based on a calibration curve prepared in advance. .
Measuring device: “HLC-8320GPC” (manufactured by Tosoh Corporation)
Analysis column: “α” + “α-M” + “α-M” (both manufactured by Tosoh Corporation)

[Volume Median Particle Size (D ₅₀ ) and CV Value of Resin Particles, Colorant Particles, and Wax Particles]
(1) Measuring apparatus: Laser diffraction type particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
(2) Measurement conditions: The sample dispersion was taken in a measurement cell, distilled water was added, and the volume-median particle size (D ₅₀ ) and the volume average particle size were measured at a concentration at which the absorbance was in an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Solid concentration of resin particle dispersion, colorant dispersion, and wax particle dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Scientific Laboratory Co., Ltd.), a measurement sample 5 g was dried at a temperature of 150 ° C., a measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of moisture content 0.05% ), Moisture (mass%) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-water content (% by mass)

[Volume-median particle size of the aggregated particles _{(D 50)]}
The volume-median particle size (D ₅₀ ) of the aggregated particles was measured as follows.
Measuring instrument: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
Electrolyte: “Isoton (registered trademark) II” (Beckman Coulter, Inc.)
Measurement conditions: After adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte, 30,000 particles are measured again, and the particle size The volume-median particle size (D ₅₀ ) was determined from the distribution.

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

[Volume Median Particle Size (D ₅₀ ) and CV Value of Toner Particles]
The volume median particle size (D ₅₀ ) of the toner particles was measured as follows.
The measuring device, aperture diameter, analysis software, and electrolyte used were the same as those used in the measurement of the volume-median particle size (D ₅₀ ) of the aggregated particles.
Dispersion: Polyoxyethylene lauryl ether “Emalgen (registered trademark) 109P” (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) is dissolved in the electrolytic solution, and the dispersion has a concentration of 5% by mass. Got.
Dispersion condition: 10 mg of a measurement sample of toner particles after drying is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte is added, and further with an ultrasonic disperser. A sample dispersion was prepared by dispersing for 1 minute.
Measurement conditions: After adding the sample dispersion to 100 mL of the electrolyte 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 (D ₅₀ ) and the volume average particle size were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Evaluation]
[Durability (time until streaks)]
Toner is mounted on an ID cartridge of a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Co., Ltd.) equipped with an ID cartridge modified so that the developing roller can be seen visually. Under the condition of 80% humidity, run at 70 r / min (equivalent to 36 sheets / min), observe the occurrence of uneven stripes on the surface of the developing roller, and measure the time until the occurrence of uneven stripes, It was used as an index of durability. The larger the value, the better the durability.
In addition, the unevenness refers to a state where the amount of toner adhering to the developing roller varies, and due to the occurrence of unevenness, shading occurs in the image density during printing.

[Coloring power (image density of printed matter)]
Using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Corporation) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.30 ± 0. A solid image of 0.01 mg / cm ² was output.
Next, the temperature of the fixing device was set to 150 ° C., and the toner was fixed at a speed of 1.7 seconds per sheet in the A4 longitudinal direction to obtain a printed matter.
30 sheets of high quality paper “Excellent White Paper A4 Size” (Oki Data Co., Ltd.) is laid under the printed material, and the reflected image density of the solid image portion of the printed material is measured with a colorimeter “SpectroEye” (manufactured by GretagMacbeth, Hikari Shooting conditions: standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and measured values of 10 arbitrary points on the image were averaged to obtain an image density. The larger the value, the better the image density and the higher the coloring power of the toner.

[Production of resin]
Production Example A1 (Production of Amorphous Resin A-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3325 g of a polyoxypropylene (2.2) adduct of bisphenol A, poly of bisphenol A 3088 g of oxyethylene (2.2) adduct, 1798 g of terephthalic acid, 255 g of dodecenyl succinic anhydride, 28 g of di (2-ethylhexanoic acid) tin (II), and 2.8 g of 3,4,5-trihydroxybenzoic acid The flask was heated to 235 ° C. with stirring in a nitrogen atmosphere and held at 235 ° C. for 10 hours, and then the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, it cools to 190 degreeC, Trimellitic anhydride 730g is added, and it heats up to 220 degreeC at 10 degreeC / hr, Then, the pressure in a flask is lowered | hung and desired kPa at 10 kPa Reaction was performed to the softening point and amorphous resin A-1 was obtained. The physical properties are shown in Table 1.

[Production of Compound B]
Production Example B1 (Production of Compound B-1)
Into a 2 L four-necked flask equipped with a cooling pipe, a nitrogen introducing pipe, a stirrer, a dehydrating pipe and a thermocouple, 20 g of “polyethyleneimine 1200” (manufactured by Junsei Chemical Co., Ltd.) as a basic nitrogen-containing group raw material, As a halogenated alkane, 92 g of 1-chlorodocosane (manufactured by Tokyo Chemical Industry Co., Ltd.), 55 g of potassium carbonate fine powder (manufactured by Wako Pure Chemical Industries, Ltd.), and 212 g of ultra-dehydrated acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) are added, and nitrogen is added. The inside of the reaction vessel was replaced with gas. The reaction vessel was heated to 80 ° C. and held for 200 hours, and then the solvent was distilled off under reduced pressure. The proton peak (3.5 to 3.6 ppm) at the terminal of the halogenated alkane was analyzed by ¹ H-NMR analysis. It confirmed that the reaction rate was 95% or more from the residual rate, and obtained compound B-1. The physical properties are shown in Table 2.

Production Example B2 (Production of Compound B-2)
Compound B-2 was obtained in the same manner as in Production Example B1, except that the types and amounts of the basic nitrogen-containing base material, halogenated alkane, potassium carbonate fine powder, and ultra-dehydrated acetonitrile were changed as shown in Table 2. It was. The physical properties are shown in Table 2.

[Production of toner]
Example 1 (Production of Toner 1)
In a Henschel mixer, 100 parts by mass of amorphous resin A-1, 4 parts by mass of compound B-1, and 10 parts by mass of yellow pigment “Toner Yellow HG” (CI Pigment Yellow 180, manufactured by Clariant Chemicals Co., Ltd.) , Fischer-Tropsch wax “FT-115” (manufactured by Nippon Seiwa Co., Ltd., melting point: 105 ° C.) 8 parts by mass, negative charge control agent “Bontron E-81” (manufactured by Orient Chemical Co., Ltd.) 0.2 mass After mixing and mixing, the mixture was melt kneaded using the same-direction rotating twin screw extruder “PCM-30” (Ikegai Co., Ltd., shaft diameter 2.9 cm, shaft cross-sectional area 7.06 cm ² ). Operating conditions are barrel set temperature 110 ° C., shaft rotation speed 200 r / min (shaft rotation peripheral speed 0.30 m / sec), mixture supply speed 10 kg / h (mixture supply amount per unit cross-sectional area of shaft 1.42 kg) / H · cm ² ). The obtained melt-kneaded product was cooled, coarsely pulverized with a rotoplex, pulverized with a jet mill, classified with an airflow classifier, and a volume-median particle size (D ₅₀ ) of 6.0 μm, CV value of 30%. Toner particles were obtained.
100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica “Cabosil (registered trademark) TS720” (Cabot Japan) 1.0 part by mass (manufactured by Co., Ltd., number average particle size; 0.012 μm) was placed in a Henschel mixer and stirred, and passed through a 150-mesh sieve to obtain toner 1. Table 3 shows the evaluation results of the obtained toner.

Examples 2 to 10 and Comparative Examples 1 to 4 (Production of Toners 2 to 10 and 51 to 54)
As shown in Table 3, toners 2 to 10, 51 to 54 were obtained in the same manner as in Example 1 except that the types and amounts of the amorphous resin, compound B, wax, and colorant were changed. Table 3 shows the evaluation results of the obtained toner.

  From the above Examples and Comparative Examples, it can be seen that the toner containing an amorphous resin having an acidic group, a colorant, a wax, and Compound B exhibits excellent durability and coloring power.

Claims (8)

  From an amorphous resin having an acidic group, a colorant, a wax, an aliphatic hydrocarbon group having 12 to 30 carbon atoms, and an amino group, imino group, cyano group, azo group, diazo group, and adi group A toner for developing an electrostatic charge image, comprising: Compound B having at least one basic nitrogen-containing group selected from the group consisting of:   The electrostatic image developing toner according to claim 1, wherein the compound B is dispersed in the amorphous resin.   The electrostatic image developing toner according to claim 1, wherein the colorant is an azo compound.   The electrostatic image developing toner according to claim 1, wherein the wax is at least one selected from the group consisting of a hydrocarbon wax and an ester wax.   The electrostatic image developing toner according to claim 1, wherein the basic nitrogen-containing group is an amino group.   The electrostatic image developing toner according to claim 1, wherein the compound B is a reaction product of a basic nitrogen-containing group material and an aliphatic hydrocarbon group material.   The electrostatic image developing toner according to claim 1, wherein the amorphous resin is a polyester resin. From an amorphous resin having an acidic group, a colorant, a wax, an aliphatic hydrocarbon group having 12 to 30 carbon atoms, and an amino group, imino group, cyano group, azo group, diazo group, and adi group A step of heat-treating in the presence of compound B having at least one basic nitrogen-containing group selected from the group consisting of:
A method for producing a toner for developing an electrostatic charge image, wherein a maximum temperature in the heat treatment step is not less than a temperature 10 ° C. lower than the melting point of the compound B and not more than 100 ° C. higher than the melting point of the compound B.