JP2017015962A - Toner for electrostatic charge image development and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development which is excellent in low temperature fixability and storage property and can suppress energy consumption when a toner is produced.SOLUTION: There is provided a toner for electrostatic charge image development which contains three or more kinds of elements selected from at least an iron element, a silicon element and a sulfur element from the group consisting of the iron element, the silicon element, the sulfur element and a fluorine element, where a content of the iron element is 1.0×10to 1.0×10ppm, a content of the silicon element is 1.0×10to 5.0×10ppm, a content of the sulfur element is 500-3,000 ppm, and a content of the fluorine element is 1.0×10to 1.0×10ppm when the fluorine element is contained, a binder resin contains at least an amorphous polyester resin, and the amorphous polyester resin has (1) a concentration of an aromatic ring of 4.5-5.8 mol/kg, (2) a weight average molecular weight (Mw) of 7,000-50,000, and (3) a glass transition temperature (Tg) of 50-70°C.SELECTED DRAWING: None

Description

  The present invention relates to an electrostatic charge image developing toner and a method for producing the same.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, after the surface of the photoreceptor is uniformly charged, an electrostatic charge image is formed on the surface of the photoreceptor, and the electrostatic latent image is developed with a developer containing toner, and visualized as a toner image. The toner image is transferred and fixed on the surface of the recording medium to form an image. As the developer used here, a two-component developer composed of a toner and a carrier and a one-component developer using a magnetic toner or a nonmagnetic toner alone are known.

  In recent years, from the viewpoint of energy saving, in order to reduce power consumption, it is required to fix a toner image at a low temperature. In order to fix at a low temperature, for example, measures are taken to lower the glass transition temperature of the binder resin of the toner.

  As a method for producing toner, conventionally, a kneading and pulverizing method is used in which a thermoplastic resin is melt-kneaded together with a colorant such as a pigment, a charge control agent, and a release agent such as wax, and after cooling, pulverized and classified. It was. However, in the usual kneading and pulverizing method, the toner shape and the toner surface structure are indefinite. For this reason, the reliability of the developer is deteriorated, such as charge deterioration, toner scattering, and image quality deterioration due to a decrease in developability. For this reason, in recent years, a toner production method using an emulsion polymerization aggregation method capable of controlling the intentional toner shape and toner surface structure has been proposed (for example, Patent Document 1 and Patent Document 2). In this toner production method, a resin fine particle dispersion prepared by emulsion polymerization or the like and a colorant particle dispersion in which a colorant is dispersed in a solvent are mixed at least to form an aggregate corresponding to the toner particle size. Thereafter, the aggregates are fused and united by heating to obtain toner particles having a desired particle diameter. This toner manufacturing method not only makes it easy to reduce the diameter of toner particles, but also makes it possible to obtain an extremely excellent toner in particle size distribution.

  As a toner binder resin, a polyester resin excellent in fixability and storage stability is generally used. Usually, polyester resins need to be synthesized at a high temperature of 200 ° C. or higher. However, in recent years, polymerization of polyester resins at low temperatures has been studied in order to reduce energy consumed in the toner production process from the viewpoint of reducing environmental impact. ing.

Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439

  As described above, in order to fix at a low temperature, measures are taken to lower the glass transition temperature of the binder resin of the toner. However, if the glass transition temperature of the binder resin of the toner is lowered, the toner is transferred in the printer or during transportation. Precipitates deteriorate due to aggregation.

  Further, as described above, polymerization of polyester resins at low temperatures has been studied. However, conventional toners using low-temperature polymerization polyester resins cannot satisfy low-temperature fixability and storage stability.

  For this reason, the present invention has been made in view of the above-described problems, and is an electrostatic charge image developing toner that is excellent in low-temperature fixability and storability, and that can suppress energy consumption during toner production, and its toner An object is to provide a manufacturing method.

The inventor has intensively studied to achieve the above-described object, and controls the aromatic ring concentration, weight average molecular weight and glass transition temperature of the polyester resin used as the binder resin, and further controls the amount of metal in the toner. As a result, the inventors have found that an electrostatic charge image developing toner excellent in low-temperature fixability and storage stability can be obtained.
Also, during the synthesis of the polyester resin used as the binder resin, by adjusting the monomer type and blending ratio, and further adjusting the type of catalyst to suppress the synthesis temperature to 150 ° C. or less, the binder resin is synthesized. It has come to the knowledge that the energy consumption can be greatly reduced.

  This invention is made | formed based on this knowledge, and has the following structures.

(Configuration 1)
In the electrostatic image developing toner comprising at least a binder resin,
Including at least three elements selected from the group consisting of iron element, silicon element, sulfur element and fluorine element, including at least iron element, silicon element and sulfur element,
The content of the iron element is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, the content of the silicon element is 1.0 × 10 ^{3 to} 5.0 × 10 ³ ppm, and the sulfur When the content of the element is 500 to 3000 ppm and the fluorine element is included, the content of the fluorine element is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm,
The binder resin includes at least an amorphous polyester resin,
The amorphous polyester resin is
(1) The aromatic ring concentration is 4.5 to 5.8 mol / kg,
(2) The weight average molecular weight (Mw) is 7000-50000,
(3) The glass transition temperature (Tg) is 50 to 70 ° C.,
(4) An electrostatic charge image developing toner that satisfies Formula 1 when the weight average molecular weight (Mw) is 7000 or more and less than 14000, and satisfies Formula 2 when the weight average molecular weight (Mw) is 14000 or more and 50000 or less.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

(Configuration 2)
The non-crystalline polyester resin includes a structure derived from a polycarboxylic acid component in a repeating unit, and the polycarboxylic acid component has a substituent corresponding to three or more carboxyl groups. Toner for charge image development.

（式（１）中、
Ｒ１は水素原子、カルボキシル基、置換もしくは無置換の直鎖状脂肪族炭化水素基、置換もしくは無置換の分岐状脂肪族炭化水素基、置換もしくは無置換の環状脂肪族炭化水素基、または置換もしくは無置換の芳香族炭化水素基であり、
Ｒ２はカルボニル基、スルホニル基または酸素原子であり、
Ｂは、置換もしくは無置換の直鎖状脂肪族炭化水素基、置換もしくは無置換の分岐状脂肪族炭化水素基、置換もしくは無置換の環状脂肪族炭化水素基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換のジフェニルメチル基、置換もしくは無置換の直鎖状脂肪族炭化水素基を両端に有しかつエステル結合を内側に有する官能基、置換もしくは無置換の直鎖状脂肪族炭化水素基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基、置換もしくは無置換の分岐状脂肪族炭化水素基を両端に有しかつエステル結合を内側に有する官能基、置換もしくは無置換の分岐状脂肪族炭化水素基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基、置換もしくは無置換の環状脂肪族炭化水素基を両端に有しかつエステル結合を内側に有する官能基、置換もしくは無置換の環状脂肪族炭化水素基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基、置換もしくは無置換の芳香族炭化水素基を両端に有しかつエステル結合を内側に有する官能基、置換もしくは無置換の芳香族炭化水素基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基、置換もしくは無置換のジフェニルメチル基を両端に有しかつエステル結合を内側に有する官能基、または置換もしくは無置換のジフェニルメチル基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基である。）

（式（２）中、Ｃｙは飽和４〜６員環、不飽和４〜６員環またはビフェニル基であり、Ｒ１およびＢは式（１）と同義である。）

（式（３）中、Ｒ３の一方は水素原子、カルボキシル基、置換もしくは無置換の直鎖状脂肪族炭化水素基、置換もしくは無置換の分岐状脂肪族炭化水素基、置換もしくは無置換の環状脂肪族炭化水素基、または置換もしくは無置換の芳香族炭化水素基であり、Ｒ３の他方はカルボキシル基であり、Ｂは式（１）と同義である。）

（式（４）中、Ｒ３は式（３）と同義であり、Ｂは式（１）と同義である。）

（式（５）中、Ｒ３およびＢは式（１）と同義である。）

（式（６）中、Ｒ３およびＢは式（１）と同義である。）

（式（７）中、Ｄは少なくとも１つの水素原子がカルボキシル基によって置換された飽和もしくは不飽和炭化水素基であり、Ｂは式（１）と同義である。） (Configuration 3)
The electrostatic charge image developing toner according to Configuration 1 or 2, wherein the amorphous polyester-based resin includes a repeating unit represented by any one of General Formulas (1) to (7).

(In the formula (1),
R1 represents a hydrogen atom, a carboxyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic aliphatic hydrocarbon group, or a substituted or unsubstituted An unsubstituted aromatic hydrocarbon group,
R2 is a carbonyl group, a sulfonyl group or an oxygen atom,
B represents a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic aliphatic hydrocarbon group, a substituted or unsubstituted aromatic carbon group. A functional group having a hydrogen group, a substituted or unsubstituted diphenylmethyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group at both ends and an ester bond inside, a substituted or unsubstituted linear aliphatic A functional group having a hydrocarbon group at both ends and having an ester bond and a urethane bond inside, a functional group having a substituted or unsubstituted branched aliphatic hydrocarbon group at both ends and an ester bond inside, substituted or A functional group having an unsubstituted branched aliphatic hydrocarbon group at both ends and an ester bond and a urethane bond inside, and a substituted or unsubstituted cyclic aliphatic hydrocarbon group at both ends A functional group having an ester bond inside, a substituted or unsubstituted cyclic aliphatic hydrocarbon group at both ends, and a functional group having an ester bond and a urethane bond inside, a substituted or unsubstituted aromatic hydrocarbon group A functional group having an ester bond inside, a substituted or unsubstituted aromatic hydrocarbon group at both ends, and a functional group having an ester bond and a urethane bond inside, substituted or unsubstituted diphenylmethyl A functional group having a group at both ends and an ester bond inside, or a functional group having a substituted or unsubstituted diphenylmethyl group at both ends and an ester bond and a urethane bond inside. )

(In formula (2), Cy is a saturated 4- to 6-membered ring, an unsaturated 4- to 6-membered ring, or a biphenyl group, and R1 and B have the same meanings as in formula (1).)

(In the formula (3), one of R3 is a hydrogen atom, a carboxyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic group. An aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group, the other of R3 is a carboxyl group, and B is as defined in Formula (1).)

(In Formula (4), R3 is synonymous with Formula (3), and B is synonymous with Formula (1).)

(In Formula (5), R3 and B are synonymous with Formula (1).)

(In Formula (6), R3 and B are synonymous with Formula (1).)

(In formula (7), D is a saturated or unsaturated hydrocarbon group in which at least one hydrogen atom is substituted with a carboxyl group, and B has the same meaning as in formula (1).)

(Configuration 4)
The toner for developing an electrostatic charge image according to Configuration 3, wherein when B has a substituent, the substituent is a hydrocarbon group having 1 to 10 carbon atoms.

(Configuration 5)
The toner for developing an electrostatic charge image according to Configuration 3 or 4, wherein the amorphous polyester resin contains 0.02 to 0.35 mol / kg of the repeating unit.

(Configuration 6)
The binder resin includes a crystalline polyester resin,
The crystalline polyester resin is
(A) The endothermic amount upon melting by differential scanning calorimetry is 2.0-10.0 W / g,
(B) The weight average molecular weight is 5000-15000,
(C) In the endothermic curve in differential scanning calorimetry, the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature is 3 to 5 ° C.,
(D) including one or more elements selected from sulfur element and fluorine element including at least sulfur element,
(E) The toner for developing an electrostatic charge image according to any one of constitutions 1 to 5, wherein the content of the weight average molecular weight of 1000 or less is 1 to less than 10%.

(Configuration 7)
A coating layer is provided on the outer surface,
The electrostatic charge image developing toner according to any one of configurations 1 to 6, wherein the coating layer contains at least the amorphous polyester resin.

(Configuration 8)
The electrostatic image developing toner according to Configuration 7, wherein the coating layer has a thickness of 0.2 to 1.0 μm.

(Configuration 9)
9. The electrostatic charge image developing toner according to any one of constitutions 1 to 8, wherein the toner has an acid value of 3 to 25 mg KOH / g.

(Configuration 10)
Having a volume average particle size of 3-9 μm,
The number of particles having a number average particle diameter of 3 μm or less is 3% by number or less,
The static according to any one of the constitutions 1 to 9, wherein the ratio of the abundance of the particles having a particle diameter of 3 μm or less to the abundance of the particles having a number average particle diameter of 1 μm or less is 2.0 to 4.0. Toner for charge image development.

(Configuration 11)
In a method for producing an electrostatic charge image developing toner comprising at least a binder resin,
The first polycarboxylic acid component and the polyol component are subjected to dehydration condensation in the presence of a catalyst at a temperature of 150 ° C. or lower, (i) the resin obtained by the dehydration condensation is urethane-extended in the presence of the polyisocyanate component, and then Elongate with a second polycarboxylic acid component having a substituent corresponding to 3 or more carboxyl groups to synthesize an amorphous polyester resin, or (ii) 3 resins obtained by dehydration condensation An amorphous polyester resin is synthesized by extending with a second polycarboxylic acid component having a substituent corresponding to one or more carboxyl groups, and then extending with urethane in the presence of a polyisocyanate component. A polyester resin synthesis step;
An amorphous polyester resin latex forming step of forming a latex of the amorphous polyester resin;
A crystalline polyester resin synthesis step of synthesizing a crystalline polyester resin by dehydrating and condensing an aliphatic polycarboxylic acid component and an aliphatic polyol component at a temperature of 100 ° C. or lower in the presence of a catalyst;
A crystalline polyester resin latex forming step for forming a latex of the crystalline polyester resin;
A mixed liquid forming step of mixing at least the amorphous polyester resin latex and the crystalline polyester resin latex to form a mixed liquid;
A primary agglomerated particle forming step of adding a flocculant to the mixed solution, aggregating the amorphous polyester resin and the crystalline polyester resin to form primary agglomerated particles;
A coated aggregated particle forming step of forming a coated aggregated particle by providing a coating layer formed from the amorphous polyester-based resin on the surface of the primary aggregated particle;
Fusing and coalescing the coated agglomerated particles at a temperature higher than the glass transition temperature of the amorphous polyester resin,
The amorphous polyester resin is
(1) The aromatic ring concentration is 4.5 to 5.8 mol / kg,
(2) The weight average molecular weight (Mw) is 7000-50000,
(3) Glass transition temperature (Tg) is 42.0-68.4 degreeC,
(4) When the weight average molecular weight (Mw) is 7000 or more and less than 14,000, the formula 1 is satisfied, and when the weight average molecular weight (Mw) is 14,000 or more and 50000 or less, the formula 2 is satisfied,
The crystalline polyester resin is
(A) The endothermic amount upon melting by differential scanning calorimetry is 2.0-10.0 W / g,
(B) The weight average molecular weight is 5000-15000,
(C) In the endothermic curve in differential scanning calorimetry, the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature is 3 to 5 ° C.,
(D) including one or more elements selected from sulfur element and fluorine element including at least sulfur element,
(E) The content of the weight average molecular weight of 1000 or less is less than 1 to 10%,
The catalyst contains at least one element selected from elemental sulfur and elemental fluorine including at least elemental sulfur,
The method for producing a toner for developing an electrostatic charge image, wherein the flocculant contains an iron element and a silicon element.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

As described above, the electrostatic charge image developing toner according to the present invention is selected from the group consisting of iron element, silicon element, sulfur element and fluorine element, containing at least iron element, silicon element and sulfur element. It contains more than seed elements, the iron element content is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, and the silicon element content is 1.0 × 10 ^{3 to} 5.0 × 10 ³ ppm. When the sulfur element content is 500 to 3000 ppm and the fluorine element is contained, the fluorine element content is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, and the binder resin is at least The amorphous polyester-based resin includes (1) an aromatic ring concentration of 4.5 to 5.8 mol / kg, and (2) a weight average molecular weight (Mw) of 7,000 to 50,000. Yes, (3) Glass transition temperature Tg) is 50 to 70 ° C., (4) When the weight average molecular weight (Mw) is 7000 or more and less than 14000, Formula 1 is satisfied, and when the weight average molecular weight (Mw) is 14000 or more and 50000 or less, Formula 2 is satisfied. . For this reason, it is possible to obtain a toner for developing an electrostatic charge image that is excellent in low-temperature fixability and storage stability and can suppress energy consumption during toner production.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

According to the method for producing a toner for developing an electrostatic charge image according to the present invention, the first polycarboxylic acid component and the polyol component are subjected to dehydration condensation at a temperature of 150 ° C. or less in the presence of a catalyst, and (i) dehydration The resin obtained by the condensation is urethane-extended in the presence of a polyisocyanate component, and then stretched by a second polycarboxylic acid component having a substituent corresponding to three or more carboxyl groups to form an amorphous polyester system Or (ii) extending the resin obtained by dehydration condensation with a second polycarboxylic acid component having a substituent corresponding to three or more carboxyl groups, and then in the presence of a polyisocyanate component Elongate urethane to synthesize amorphous polyester resin, forming amorphous polyester resin synthesis process, and forming amorphous polyester resin latex A crystalline polyester resin for synthesizing a crystalline polyester resin by dehydrating and condensing an amorphous polyester resin latex forming step and an aliphatic polycarboxylic acid component and an aliphatic polyol component at a temperature of 100 ° C. or lower in the presence of a catalyst. A mixed liquid formation that forms a mixed liquid by mixing a synthetic process, a crystalline polyester resin latex forming process for forming a latex of a crystalline polyester resin, and at least an amorphous polyester resin latex and a crystalline polyester resin latex A step of adding a flocculant to the mixed liquid, aggregating the amorphous polyester resin and the crystalline polyester resin to form primary agglomerated particles, and forming a primary agglomerated particle on the surface of the primary agglomerated particles. Coated agglomerated particles that are provided with a coating layer formed from a crystalline polyester resin to form coated agglomerated particles A non-crystalline polyester resin comprising: a forming step and a coalescing and coalescing step of coalescing the coated aggregated particles at a temperature higher than the glass transition temperature of the amorphous polyester resin. Is 4.5 to 5.8 mol / kg, (2) the weight average molecular weight (Mw) is 7000 to 50000, (3) the glass transition temperature (Tg) is 50 to 70 ° C., and (4) the weight. When the average molecular weight (Mw) is 7000 or more and less than 14000, Formula 1 is satisfied, and when the weight average molecular weight (Mw) is 14000 or more and 50000 or less, Formula 2 is satisfied. The crystalline polyester resin is (A) differential scanning calorimetry. The endothermic amount at the time of melting is 2.0 to 10.0 W / g, (B) the weight average molecular weight is 5000 to 15000, and (C) the endothermic curve in the differential scanning calorimetry, The difference between the heat initiation temperature and the endothermic peak temperature is 3 to 5 ° C., (D) contains one or more elements selected from sulfur element and fluorine element including at least sulfur element, and (E) weight average molecular weight 1000 The following content is 1 to less than 10%, the catalyst contains one or more elements selected from at least sulfur element and sulfur element, and the flocculant contains iron element and silicon element . Therefore, it is possible to produce a toner for developing an electrostatic charge image that is excellent in low-temperature fixability and storage stability and can suppress energy consumption during the production of the toner.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

  Hereinafter, embodiments of the present invention will be specifically described. In addition, the following embodiment is one form at the time of actualizing this invention, Comprising: This invention is not limited within the range.

A. Toner for developing an electrostatic charge image The toner for developing an electrostatic charge image of this embodiment contains a binder resin. As the binder resin, an amorphous polyester resin having the following characteristics (1) to (4) is used. In this specification, this polyester resin is referred to as a first polyester resin.
(1) The aromatic ring concentration is 4.5 to 5.8 mol / kg.
(2) A weight average molecular weight (Mw) is 7000-50000.
(3) Glass transition temperature (Tg) is 50-70 degreeC.
(4) When the weight average molecular weight (Mw) is 7000 or more and less than 14,000, the expression 1 is satisfied, and when the weight average molecular weight (Mw) is 14000 or more and 50000 or less, the expression 2 is satisfied.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

The characteristic (1) of the first polyester resin is obtained by adjusting the types of polycarboxylic acid component, polyol component and polyisocyanate component used as monomers, and the blending ratio of the polycarboxylic acid component, polyol component and polyisocyanate component. Can be controlled.
As described above, the aromatic ring concentration of the first polyester resin is 4.5 to 5.8 mol / kg, and preferably 4.5 to 5.5. When the aromatic ring concentration is 4.5 to 5.8 mol / kg, an electrostatic charge image developing toner excellent in low temperature fixability and storage stability can be obtained. When the aromatic ring concentration exceeds 5.8 mol / kg, the low-temperature fixability deteriorates, which is not preferable. When the aromatic ring concentration is less than 4.5 mol / kg, storage stability is deteriorated, which is not preferable.
The aromatic ring concentration of the first polyester resin can be determined by analyzing the ultraviolet absorption spectrum, as will be described later.

The characteristic (2) of the first polyester resin can be controlled by adjusting the types of the polycarboxylic acid component and the polyol component used as monomers and the blending ratio of the polycarboxylic acid component and the polyol component.
As described above, the weight average molecular weight (Mw) of the first polyester resin is 7000 to 50000, and preferably 10000 to 43000. When the weight average molecular weight is 7,000 to 50,000, an electrostatic charge image developing toner excellent in low-temperature fixability and storage stability can be obtained. When the weight average molecular weight (Mw) exceeds 50,000, the low-temperature fixability is deteriorated. When the weight average molecular weight (Mw) is less than 7000, the storage stability is deteriorated, which is not preferable.
The weight average molecular weight of the first polyester resin can be determined by gel permeation chromatography (GPC) measurement as described later.

The characteristic (3) of the first polyester resin is obtained by adjusting the types of polycarboxylic acid component, polyol component and polyisocyanate component used as monomers, and the blending ratio of the polycarboxylic acid component, polyol component and polyisocyanate component. Can be controlled.
As described above, the glass transition temperature (Tg) of the first polyester resin is 50 to 70 ° C., and preferably 55 to 65 ° C. When the glass transition temperature (Tg) is from 50 to 70 ° C., an electrostatic charge image developing toner excellent in low-temperature fixability and storage stability can be obtained. If the glass transition temperature (Tg) exceeds 70 ° C., the low-temperature fixability deteriorates, which is not preferable. When the glass transition temperature (Tg) is less than 50 ° C., storage stability and chargeability deteriorate, which is not preferable.
The glass transition temperature of the first polyester resin can be determined from a differential scanning calorimetry curve obtained by differential scanning calorimetry measurement, as will be described later.

The characteristic (4) of the first polyester resin is obtained by adjusting the types of polycarboxylic acid component, polyol component and polyisocyanate component used as monomers, and the blending ratio of the polycarboxylic acid component, polyol component and polyisocyanate component. Can be controlled.
The weight average molecular weight and glass transition temperature of the first polyester resin satisfy the formula 1 when the weight average molecular weight (Mw) is 7000 or more and less than 14000, and the weight average molecular weight (Mw) is 14000 or more and 50000 or less. 2 is satisfied. When Formula 1 or Formula 2 is satisfied, an electrostatic charge image developing toner excellent in low-temperature fixability and storage stability can be obtained.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

（式（１）中、Ｒ１は水素原子、カルボキシル基、置換もしくは無置換の直鎖状脂肪族炭化水素基、置換もしくは無置換の分岐状脂肪族炭化水素基、置換もしくは無置換の環状脂肪族炭化水素基、または置換もしくは無置換の芳香族炭化水素基である。Ｒ２はカルボニル基、スルホニル基または酸素原子である。Ｂは、置換もしくは無置換の直鎖状脂肪族炭化水素基、置換もしくは無置換の分岐状脂肪族炭化水素基、置換もしくは無置換の環状脂肪族炭化水素基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換のジフェニルメチル基、置換もしくは無置換の直鎖状脂肪族炭化水素基を両端に有しかつエステル結合を内側に有する官能基、置換もしくは無置換の直鎖状脂肪族炭化水素基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基、置換もしくは無置換の分岐状脂肪族炭化水素基を両端に有しかつエステル結合を内側に有する官能基、置換もしくは無置換の分岐状脂肪族炭化水素基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基、置換もしくは無置換の環状脂肪族炭化水素基を両端に有しかつエステル結合を内側に有する官能基、置換もしくは無置換の環状脂肪族炭化水素基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基、置換もしくは無置換の芳香族炭化水素基を両端に有しかつエステル結合を内側に有する官能基、置換もしくは無置換の芳香族炭化水素基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基、置換もしくは無置換のジフェニルメチル基を両端に有しかつエステル結合を内側に有する官能基、または置換もしくは無置換のジフェニルメチル基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基である。すなわち、Ｂは置換もしくは無置換の直鎖状脂肪族炭化水素基、置換もしくは無置換の分岐状脂肪族炭化水素基、置換もしくは無置換の環状脂肪族炭化水素基、置換もしくは無置換の芳香族炭化水素基、または置換もしくは無置換のジフェニルメチル基である場合（以下、第１の官能基と称する）であってもよいし、第１の官能基を両端に有しかつエステル結合を内側（すなわち、両端の間）に有する官能基である場合であってもよいし、第１の官能基を両端に有しかつエステル結合およびウレタン結合を内側に有する官能基である場合であってもよい。また、Ｂが置換基をもつ場合、その置換基は炭素数１から１０の炭化水素基であることが好ましい。）

（式（２）中、Ｃｙ飽和４〜６員環、不飽和４〜６員環またはビフェニル基であり、Ｒ１およびＢは式（１）と同義である。）

（式（３）中、Ｒ３の一方は水素原子、カルボキシル基、置換もしくは無置換の直鎖状脂肪族炭化水素基、置換もしくは無置換の分岐状脂肪族炭化水素基、置換もしくは無置換の環状脂肪族炭化水素基、または置換もしくは無置換の芳香族炭化水素基であり、Ｒ３の他方はカルボキシル基であり、Ｂは式（１）と同義である。）

（式（４）中、Ｒ３は式（３）と同義であり、Ｂは式（１）と同義である。）

（式（５）中、Ｒ３およびＢは式（１）と同義である。）

（式（６）中、Ｒ３およびＢは式（１）と同義である。）

（式（７）中、Ｄは少なくとも１つの水素原子がカルボキシル基によって置換された飽和もしくは不飽和炭化水素基であり、Ｂは式（１）と同義である。） It is preferable that a 1st polyester resin contains the repeating unit represented by either of the following general formula (1)-(7). The repeating units represented by the general formulas (1) to (7) have a carboxyl group in the side chain. For this reason, when the repeating unit represented by the general formulas (1) to (7) is included, the glass transition temperature can be controlled to 50 to 70 ° C.

(In the formula (1), R1 is a hydrogen atom, a carboxyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic aliphatic. A hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, R2 is a carbonyl group, a sulfonyl group, or an oxygen atom, B is a substituted or unsubstituted linear aliphatic hydrocarbon group, substituted or unsubstituted Unsubstituted branched aliphatic hydrocarbon group, substituted or unsubstituted cyclic aliphatic hydrocarbon group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted diphenylmethyl group, substituted or unsubstituted straight chain A functional group having an ester-like aliphatic hydrocarbon group at both ends and an ester bond inside, a substituted or unsubstituted linear aliphatic hydrocarbon group at both ends, and an ester bond and urea A functional group having an inner bond, a substituted or unsubstituted branched aliphatic hydrocarbon group at both ends and a functional group having an ester bond on the inner side, a substituted or unsubstituted branched aliphatic hydrocarbon group at both ends A functional group having an ester bond and a urethane bond inside, a substituted or unsubstituted cyclic aliphatic hydrocarbon group at both ends and an ester bond inside, a substituted or unsubstituted cyclic aliphatic Functional group having a hydrocarbon group at both ends and having an ester bond and urethane bond inside, a functional group having a substituted or unsubstituted aromatic hydrocarbon group at both ends and having an ester bond inside, substituted or unsubstituted A functional group having an aromatic hydrocarbon group at both ends and an ester bond and a urethane bond inside, a substituted or unsubstituted diphenylmethyl group at both ends And a functional group having an ester bond inside, or a functional group having a substituted or unsubstituted diphenylmethyl group at both ends and an ester bond and a urethane bond inside, that is, B is a substituted or unsubstituted straight chain. Chain aliphatic hydrocarbon group, substituted or unsubstituted branched aliphatic hydrocarbon group, substituted or unsubstituted cyclic aliphatic hydrocarbon group, substituted or unsubstituted aromatic hydrocarbon group, or substituted or unsubstituted It may be a diphenylmethyl group (hereinafter referred to as a first functional group), or a functional group having a first functional group at both ends and an ester bond inside (that is, between both ends). Or a functional group having a first functional group at both ends and having an ester bond and a urethane bond inside, and B is When it has a substituent, the substituent is preferably a hydrocarbon group having 1 to 10 carbon atoms. )

(In Formula (2), it is a Cy saturated 4-6 membered ring, an unsaturated 4-6 membered ring, or a biphenyl group, and R1 and B are synonymous with Formula (1).)

(In the formula (3), one of R3 is a hydrogen atom, a carboxyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic group. An aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group, the other of R3 is a carboxyl group, and B is as defined in Formula (1).)

(In Formula (4), R3 is synonymous with Formula (3), and B is synonymous with Formula (1).)

(In Formula (5), R3 and B are synonymous with Formula (1).)

(In Formula (6), R3 and B are synonymous with Formula (1).)

(In formula (7), D is a saturated or unsaturated hydrocarbon group in which at least one hydrogen atom is substituted with a carboxyl group, and B has the same meaning as in formula (1).)

The first polyester resin preferably contains 0.02 to 0.35 mol / kg, more preferably 0.08 to 0.3 mol / kg of the repeating units represented by the general formulas (1) to (7). . When the content of the repeating unit is 0.02 to 0.35 mol / kg, the glass transition temperature can be controlled to 50 to 70 ° C. When the content of the repeating unit exceeds 0.35 mol / kg, the glass transition temperature becomes high, which is not preferable. When the content of the repeating unit is less than 0.02 mol / kg, the glass transition temperature is lowered, which is not preferable.
The content of the repeating unit represented by the general formulas (1) to (7) of the first polyester resin is the type of polycarboxylic acid component and polyol component used as the monomer, the blending ratio of the polycarboxylic acid component and the polyol component, etc. It can be controlled by adjusting.

The first polyester resin is obtained by dehydrating and condensing the first polycarboxylic acid component and the polyol component, and (i) urethane-extending the resin obtained by the dehydrating condensation in the presence of the polyisocyanate component. What is synthesized by stretching with a polycarboxylic acid component, or (ii) A resin obtained by dehydration condensation is stretched with a second polycarboxylic acid component, and then urethane stretched in the presence of a polyisocyanate component Are synthesized.
Although there is no restriction | limiting in particular as a 1st polycarboxylic acid component which can be used for formation of a 1st polyester resin, What has a substituent corresponding to two carboxyl groups is preferable. Examples of the case of having a substituent corresponding to two carboxyl groups include the case of having two carboxyl groups and the case of having one acid anhydride group. As the first polycarboxylic acid component that can be used to form the first polyester resin, aliphatic carboxylic acids, aromatic carboxylic acids, and their acid anhydrides having substituents corresponding to two carboxyl groups Common organic polycarboxylic acids such as lower alkyl (C1-4) esters are listed. As specific examples, aliphatic (including alicyclic) dicarboxylic acids include alkane dicarboxylic acids having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, reparginic acid, and sebacic acid), carbon Examples thereof include alkene dicarboxylic acids of several 4 to 50 (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and glutaconic acid). Aromatic dicarboxylic acids include aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), their acid anhydrides and lower alkyls (1 to 4 carbon atoms). Examples include esters.
The second polycarboxylic acid component that can be used for forming the first polyester resin has a substituent corresponding to three or more carboxyl groups. When the second polycarboxylic acid component having a substituent corresponding to three or more carboxyl groups is used, the substituent corresponding to three or more carboxyl groups in the repeating unit of the first polyester resin The structure derived from the polycarboxylic acid component which has is included. Examples of the case of having a substituent corresponding to three or more carboxyl groups include, for example, the case of having three carboxyl groups, the case of having one acid anhydride group and one carboxyl group, and the case of two acids. The case where it has an anhydride group is mentioned. Examples of the second polycarboxylic acid component that can be used for forming the first polyester resin include general organic polycarboxylic acids having substituents corresponding to three or more carboxyl groups. Specific examples include trimellitic anhydride, pyromellitic anhydride, 4,4′-biphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 4- (2,5- Dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, meso-butane- 1,2,3,4-tetracarboxylic dianhydride, 1,3,5-benzenetricarboxylic acid, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 4,4′-oxydiphthalate Acid anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride Nothing , 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride . When trimellitic anhydride is used, the 1st polyester resin containing the repeating unit represented by General formula (2) is obtained. When pyromellitic anhydride is used, a first polyester resin containing a repeating unit represented by the general formula (2) is obtained. When 4,4′-biphthalic dianhydride is used, a first polyester resin containing a repeating unit represented by the general formula (2) is obtained. When 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride is used, a first polyester resin containing a repeating unit represented by the general formula (1) is obtained. When 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1-dicarboxylic acid anhydride is used, the repeating unit represented by the general formula (3) A first polyester resin containing is obtained. When naphthalene-1,4,5,8-tetracarboxylic dianhydride is used, a first polyester resin containing a repeating unit represented by the general formula (5) is obtained. When meso-butane-1,2,3,4-tetracarboxylic dianhydride is used, a first polyester resin containing a repeating unit represented by the general formula (7) is obtained. When 1,3,5-benzenetricarboxylic acid is used, a first polyester resin containing a repeating unit represented by the general formula (2) is obtained. When 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride is used, a first polyester resin containing a repeating unit represented by the general formula (1) is obtained. When 4,4′-oxydiphthalic anhydride is used, a first polyester resin containing a repeating unit represented by the general formula (1) is obtained. When 1,2,3,4-cyclopentanetetracarboxylic dianhydride is used, a first polyester resin containing a repeating unit represented by the general formula (2) is obtained. When 1,2,4,5-cyclohexanetetracarboxylic dianhydride is used, a first polyester resin containing a repeating unit represented by the general formula (2) is obtained. When 1,2,3,4-cyclobutanetetracarboxylic dianhydride is used, a first polyester resin containing a repeating unit represented by the general formula (2) is obtained. When 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride is used, the first polyester resin containing a repeating unit represented by the general formula (4) Is obtained. When 3,4,9,10-perylenetetracarboxylic dianhydride is used, a first polyester resin containing a repeating unit represented by the general formula (6) is obtained.
There is no restriction | limiting in particular as a polyol component which can be used for formation of a 1st polyester resin. Specific examples include aliphatic diols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane. Diol, 2,3-pentanediol, 1,6-hexanediol, 2,3-hexanediol, 3,4-hexanediol, neopentylglycol, 1,7-heptanediol, dodecanediol, etc.); 36 polyalkylene ether glycols (diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, etc.); C 2-4 alkylene oxides of the aliphatic diols having 2 to 36 carbon atoms (hereinafter abbreviated as AO) [ethylene oxide ( (Hereinafter abbreviated as EO), Lopylene oxide (hereinafter abbreviated as PO) and butylene oxide, etc.] Adduct (addition mole number 2-30); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.) An AO adduct having 2 to 4 carbon atoms (addition moles 2 to 30) of the alicyclic diol; an AO adduct having 2 to 4 carbon atoms (addition) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); Mole number 2-30) etc. are mentioned.
Examples of the polyisocyanate component for extending the urethane that can be used to form the first polyester resin include general organic polyisocyanate components. Specific examples include diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, toluylene diisocyanate, naphthalene diisocyanate, dibenzyldimethylmethane p, p'-diisocyanate, hexamethylene diisocyanate, norbornene diisocyanate, and the like. Examples thereof include nurate compounds and adduct bodies.

  In the electrostatic image developing toner of this embodiment, a mixture of two or more kinds of polyester resins having the above-mentioned characteristics (1) to (4) may be used as the first polyester resin.

  In the electrostatic charge image developing toner of this embodiment, it is preferable to use a crystalline polyester resin in addition to the first polyester resin as the binder resin. In the present specification, this crystalline polyester resin is referred to as a second polyester resin.

The crystalline polyester resin used as the binder resin has the following characteristics (A) to (E).
(A) The amount of heat absorbed during melting by differential scanning calorimetry (DSC) measurement is 2.0 to 10.0 W / g.
(B) The weight average molecular weight is 5000-15000.
(C) In the endothermic curve in differential scanning calorimetry, the difference between the endothermic start temperature during temperature rise and the endothermic peak temperature is 3 to 5 ° C.
(D) It contains one or more elements selected from sulfur element and fluorine element including at least sulfur element.
(E) The content of the weight average molecular weight of 1000 or less is 1 to less than 10%.

As described above, the endothermic amount during melting of the crystalline polyester resin is preferably 2.0 to 10 W / g, and more preferably 2.5 to 9.0 W / g. When the heat absorption at the time of melting is 2.0 to 10 W / g, melting of the electrostatic image developing toner can be promoted with a small amount of heat. When the endothermic amount at the time of melting exceeds 10 W / g, a large amount of heat is required for melting the crystalline polyester resin, which is not preferable. A crystalline polyester resin having an endothermic amount of less than 2.0 W / g at the time of melting is not preferred because of low crystallinity.
The weight average molecular weight of the crystalline polyester resin is 5000 to 15000 as described above. When the weight average molecular weight is less than 5,000, compatibility with the amorphous polyester resin occurs, resulting in deterioration of the storage stability of the toner. When the weight average molecular weight exceeds 15,000, the toner low-temperature fixability deteriorates.
The difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature of the crystalline polyester resin is 3 to 5 ° C. as described above. When the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature is less than 3 ° C., it is very difficult to synthesize while ensuring the productivity of the resin. When the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature exceeds 5 ° C., the toner storability deteriorates and it becomes difficult to maintain the fixing performance after long-term storage of the toner.
As described above, the crystalline polyester resin contains one or more elements selected from a sulfur element and a fluorine element as a catalyst-derived element used for synthesis at 100 ° C. or lower.
The crystalline polyester resin has a weight average molecular weight of 1000 or less and a content of 1 to less than 10%. When the content of the weight average molecular weight of 1000 or less is 10% or more, the toner heat storage property deteriorates and the toner fixing lower limit performance deteriorates after long-term storage. When the content of the weight average molecular weight is 1000 or less, the toner fixing lower limit performance deteriorates.
The amount of endotherm at the time of melting of the crystalline polyester resin and the difference between the endothermic start temperature and the endothermic peak temperature at the time of temperature rise depend on the type of polycarboxylic acid component and polyol component used as the monomer of the crystalline polyester resin It can be controlled by adjusting the blending ratio of the components. In addition, the weight average molecular weight and the content of the weight average molecular weight of 1000 or less of the crystalline polyester resin can be controlled by adjusting the reaction temperature during production, time, and the like.
The endothermic amount at the time of melting of the crystalline polyester resin and the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature can be determined from a differential scanning calorimetry curve obtained by differential scanning calorimeter measurement, as described later. Further, the weight average molecular weight and the content of the weight average molecular weight of 1000 or less of the crystalline polyester resin can be determined by gel permeation chromatography (GPC) measurement as described later. In addition, the content of elemental sulfur and elemental fluorine in the crystalline polyester resin can be measured by fluorescent X-ray analysis as described later.

The crystalline polyester resin used as the binder resin preferably has a melting point of 60 to 80 ° C, more preferably 65 to 75 ° C. When the melting point is 60 to 80 ° C., both toner storage stability and fixing property can be achieved. When the melting point exceeds 80 ° C., the toner fixing property is deteriorated, which is not preferable. If the melting point is less than 60 ° C., the storage stability is deteriorated, which is not preferable.
The melting point of the crystalline polyester resin can be controlled by adjusting the types of the polycarboxylic acid component and the polyol component used as the monomer, the blending ratio of the polycarboxylic acid component and the polyol component, and the like.
The melting point of the crystalline polyester resin can be determined from a differential scanning calorimetry curve obtained by differential scanning calorimeter measurement, as will be described later.

  When a crystalline polyester resin is used as the binder resin, the content of the crystalline polyester resin is preferably 5 to 20% by weight, more preferably 7 to 15% by weight, based on the entire binder resin. When the content of the crystalline polyester resin is 5 to 20% by weight, both toner storage stability and fixing property can be achieved. If the content of the crystalline polyester resin is more than 20% by weight, it is not preferable because the storage stability and electrical characteristics are deteriorated. When the content of the crystalline polyester resin is less than 5% by weight, the fixing property is deteriorated, which is not preferable.

The crystalline polyester resin used as the binder resin is synthesized by dehydrating and condensing a polycarboxylic acid component and a polyol component.
Examples of the polycarboxylic acid component that can be used for the synthesis of the crystalline polyester resin include aliphatic polycarboxylic acids. Specific examples include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, decanedioic acid, dodecanedioic acid and the like.
Examples of the polyol component that can be used for the synthesis of the crystalline polyester resin include aliphatic polyols. Specific examples include ethylene glycol, 1,4-butanediol, 1.6-hexanediol, 1,8-octanediol, 1.9-nonanediol, 1.10-decanediol, and the like.

The electrostatic image developing toner of this embodiment includes a coating layer formed from a binder resin on the outer surface. The coating layer is formed from the first polyester resin having the above characteristics (1) to (4).
The coating layer preferably has a thickness of 0.2 to 1.0 μm. When the thickness is less than 0.2 μm, toner heat storage property is deteriorated. When the thickness exceeds 1.0 μm, the toner fixing lower limit performance deteriorates.
The thickness of the coating layer can be measured by observing with a transmission electron microscope.

The electrostatic image developing toner according to this embodiment includes at least three elements selected from the group consisting of iron element, silicon element, sulfur element and fluorine element, including at least iron element, silicon element and sulfur element. . The content of iron element is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, the content of silicon element is 1.0 × 10 ^{3 to} 5.0 × 10 ³ ppm, and the content of sulfur element The amount is 500-3000 ppm. When elemental fluorine is included, the content of elemental fluorine is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm.
The iron element and the silicon element are components derived from a flocculant described later, the sulfur element is a component derived from a catalyst and a flocculant described later, and the fluorine element is a component derived from a catalyst described later. For this reason, the content of iron element and silicon element in the toner for developing an electrostatic charge image can be controlled by adjusting the type and amount of the coagulant used, and the content of elemental sulfur is used. The type and amount of the catalyst and the flocculant can be controlled, and the content of elemental fluorine can be controlled by adjusting the type and amount of the catalyst used.
As described above, the content of the iron element in the electrostatic image developing toner is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, preferably 1000 to 5000 ppm. When the content of iron element is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, it can be used as a toner for developing an electrostatic image. If the iron element content exceeds 1.0 × 10 ⁴ ppm, the toner physical properties become too high, which is not preferable. If the iron element content is less than 1.0 × 10 ³ ppm, toner structure formation is insufficient, which is not preferable.
As described above, the content of silicon element in the electrostatic image developing toner is 1.0 × 10 ^{3 to} 5.0 × 10 ³ ppm, and preferably 1500 to 4000 ppm. When the content of the silicon element is 1.0 × 10 ^{3 to} 5.0 × 10 ³ ppm, it can be used as a toner for developing an electrostatic image. When the content of silicon element exceeds 5.0 × 10 ³ ppm, the toner physical properties become too high, which is not preferable. If the content of silicon element is less than 1.0 × 10 ³ ppm, toner structure formation is insufficient, which is not preferable.
The content of sulfur element in the electrostatic image developing toner is 500 to 3000 ppm, preferably 1000 to 3000 ppm as described above. When the content of sulfur element is 500 to 3000 ppm, it can be used as a toner for developing an electrostatic image. If the content of elemental sulfur exceeds 3000 ppm, the toner electrical characteristics deteriorate, which is not preferable. If the sulfur element content is less than 500 ppm, toner structure formation is insufficient, which is not preferable.
When the electrostatic charge image developing toner contains a fluorine element, the content of the fluorine element in the electrostatic charge image developing toner is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm as described above. Preferably, it is 5000-8000 ppm. When the content of the elemental fluorine is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, it can be used as a toner for developing an electrostatic image. If the content of fluorine element exceeds 1.0 × 10 ⁴ ppm, the physical properties of the toner become too high, which is not preferable. If the content of the elemental fluorine is less than 1.0 × 10 ³ ppm, the physical properties of the toner are lowered, which is not preferable.
The content of each element in the electrostatic image developing toner can be measured by fluorescent X-ray analysis as described later.

The electrostatic charge image developing toner of this embodiment may contain a colorant.
As the colorant that can be used in the electrostatic image developing toner of this embodiment, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G , G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR ), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cadmium Mummer Curry Red, Antimony Zhu, Permanent Red 4R, Para Red, Phi-Sa Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake , Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue , Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid Examples include lean lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon, and mixtures thereof.

The electrostatic image developing toner according to this embodiment may contain a release agent, a charge control agent, and the like.
Examples of the release agent that can be used in the electrostatic image developing toner of this embodiment include solid paraffin wax, microwax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, and fatty acid metal salt. Waxes, fatty acid ester waxes, partially saponified fatty acid ester waxes, silicone varnishes, higher alcohols, carnauba waxes and the like. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used.
As the charge control agent usable in the electrostatic image developing toner of this embodiment, all known ones can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments , Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts and salicylic acid derivatives The metal salt of these can be mentioned. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (above, Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary Copy charge PSY VP2038 of ammonium salt, copy blue PR of triphenylmethane derivative, copy charge NEG VP2036 of quaternary ammonium salt, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR- which is a boron complex 147 (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

The toner for developing an electrostatic charge image of this embodiment preferably has an acid value of 3 to 25 mg KOH / g, more preferably 5 to 20 KOH / g. When the acid value is 3 to 25 mgKOH / g, an electrostatic image developing toner excellent in chargeability can be obtained. If the acid value exceeds 25 mgKOH / g, the charge amount becomes too high, which is not preferable. An acid value of less than 3 mgKOH / g is not preferred because it becomes difficult to charge.
The acid value of the electrostatic image developing toner can be controlled by adjusting the binder resin acid value.
The acid value of the electrostatic image developing toner can be measured by a neutralization titration method as described later.

The electrostatic charge image developing toner of this embodiment preferably has a volume average particle size of 3 to 9 μm, more preferably 2.5 to 8.5 μm. When the volume average particle diameter is 3 to 9 μm, a dense image can be easily created. When the volume average particle diameter exceeds 9 μm, it is difficult to create a dense image, which is not preferable. When the volume average particle diameter is less than 3 μm, it is not preferable because it becomes difficult to handle the toner for developing an electrostatic image.
In the electrostatic image developing toner of this embodiment, the number of particles having a number average particle diameter of 3 μm or less is preferably 3% by number or less, and more preferably 2.5% or less. is there. When the amount of particles having a particle size of 3 μm or less is 3% by number or less, an electrostatic image developing toner having a uniform particle size can be obtained. If the amount of particles having a particle size of 3 μm or less exceeds 3% by number, the variation in the particle size of the toner for developing an electrostatic image becomes large.
In the electrostatic image developing toner of this embodiment, the ratio of the abundance of particles having a particle diameter of 3 μm or less to the abundance of particles having a number average particle diameter of 1 μm or less is 2.0 to 4.0. It is preferable that there is, more preferably 2.5 to 3.5. When the ratio of the abundance of particles having a particle size of 3 μm or less to the abundance of particles having a particle size of 1 μm or less is 2.0 to 4.0, the abundance of small-diameter particles that are difficult to handle can be suppressed. If the ratio of the abundance of particles having a particle size of 3 μm or less to the abundance of particles having a particle size of 1 μm or less exceeds 4.0, the abundance of small-diameter particles difficult to handle increases, which is not preferable. If the ratio of the abundance of particles having a particle size of 3 μm or less to the abundance of particles having a particle size of 1 μm or less is less than 2.0, it is not preferable because the variation in the particle size of the electrostatic image developing toner becomes large.
The volume average particle diameter of the electrostatic image developing toner can be controlled by adjusting toner production conditions and the like. The abundance of particles having a particle size of 3 μm or less in the toner for developing an electrostatic charge image can be controlled by adjusting toner production conditions and the like. Further, the ratio of the abundance of particles having a particle size of 3 μm or less to the abundance of particles having a particle size of 1 μm or less in the toner for developing an electrostatic image can be controlled by adjusting the toner production conditions.
The volume average particle diameter of the electrostatic image developing toner can be measured by a pore electrical resistance method as described later. Further, the abundance of particles having a particle diameter of 3 μm or less in the electrostatic image developing toner can be measured by a pore electrical resistance method as described later. Further, the abundance of particles having a particle size of 1 μm or less in the electrostatic image developing toner can be measured by a dynamic light scattering method as described later.

B. Method for Producing Toner for Developing Electrostatic Image The method for producing the toner for developing an electrostatic image according to this embodiment includes an amorphous polyester resin synthesizing step, an amorphous polyester resin latex forming step, and a crystalline polyester resin. A synthesis step, a crystalline polyester resin latex formation step, a mixed liquid formation step, a primary aggregated particle formation step, a coated aggregated particle formation step, and a fusion unity step are provided.

  Hereinafter, each process will be described in detail.

1. Amorphous polyester-based resin synthesis step This amorphous polyester-based resin synthesis step involves dehydrating and condensing a first polycarboxylic acid component and a polyol component at a temperature of 150 ° C. or lower in the presence of a catalyst. The resin obtained by the condensation is urethane-extended in the presence of the polyisocyanate component, and then is elongated by the second polycarboxylic acid component to synthesize the first polyester resin, or (ii) obtained by dehydration condensation. The obtained resin is elongated by the second polycarboxylic acid component, and then urethane is elongated in the presence of the polyisocyanate component to synthesize the first polyester resin.

In the amorphous polyester-based resin forming step, a first polycarboxylic acid component, a second polycarboxylic acid component, a polyol component, and a polyisocyanate component are used as raw materials used for forming the first polyester resin.
As the first polycarboxylic acid component that can be used for forming the first polyester resin, as described above, an aliphatic carboxylic acid, an aromatic carboxylic acid having substituents corresponding to two carboxyl groups, and those Common organic polycarboxylic acids such as acid anhydrides and lower alkyl (C1-4) esters are preferred. The first polycarboxylic acid component may be one type of compound or a mixture of two or more types of compounds. The amount of the first polycarboxylic acid component used is appropriately determined in consideration of the above-described characteristics (1) to (4) of the first polyester resin. Specifically, the usage-amount of the 1st polycarboxylic acid component is 7 to 35 weight% of the whole raw material used for formation of a 1st polyester resin, Preferably, it is 10 to 30 weight%. The 1st polyester resin which has the characteristic (1)-(4) mentioned above as the usage-amount of a 1st polycarboxylic acid component is 7 to 35 weight% is compoundable. If the amount of the first polycarboxylic acid component used exceeds 35% by weight, it is difficult to control the required acid value and molecular weight, which is not preferable. If the amount of the first polycarboxylic acid component used is less than 7% by weight, it is difficult to ensure the necessary molecular weight, which is not preferable.
Examples of the second polycarboxylic acid component that can be used for forming the first polyester resin include general organic polycarboxylic acids having substituents corresponding to three or more carboxyl groups, as described above. The second polycarboxylic acid component may be one type of compound or a mixture of two or more types of compounds. The amount of the second polycarboxylic acid component used is appropriately determined in consideration of the above-described characteristics (1) to (4) of the first polyester resin. Specifically, the amount of the second polycarboxylic acid component used is 0.8 to 7.0% by weight, preferably 1.0 to 6%, based on the entire raw material used for forming the first polyester resin. .6% by weight. The 1st polyester resin which has the characteristics (1)-(4) mentioned above can be synthesize | combined that the usage-amount of a 2nd polycarboxylic acid component is 0.8 to 7.0 weight%. If the amount of the second polycarboxylic acid component used exceeds 7.0% by weight, the charge amount is too high, which is not preferable. When the amount of the second polycarboxylic acid component used is less than 0.8% by weight, the charge amount is too low, which is not preferable.
Examples of the polyol component that can be used for forming the first polyester resin include general polyols as described above. The polyol component may be a single compound or a mixture of two or more compounds. The use amount of the polyol component is appropriately determined in consideration of the above-described characteristics (1) to (4) of the first polyester resin. Specifically, the amount of the polyol component used is 55 to 80% by weight, preferably 58 to 75% by weight, based on the entire raw material used for forming the first polyester resin. The 1st polyester resin which has the characteristics (1)-(4) mentioned above as the usage-amount of a polyol component is 55 to 80 weight% is compoundable. When the amount of the polyol component used exceeds 80% by weight, it is difficult to ensure the necessary molecular weight, which is not preferable. When the amount of the polyol component used is less than 55% by weight, it is not preferable because it is difficult to control the required acid value and molecular weight.
Examples of the polyisocyanate component that can be used for forming the first polyester resin include general organic polyisocyanates as described above. The polyisocyanate component may be one type of compound or a mixture of two or more types of compounds. The amount of the polyisocyanate component used is appropriately determined in consideration of the above-described characteristics (1) to (4) of the first polyester resin. Specifically, the usage amount of the polyisocyanate component is 3 to 30% by weight, preferably 4 to 25% by weight, based on the entire raw material used for forming the first polyester resin. The 1st polyester resin which has the characteristics (1)-(4) mentioned above as the usage-amount of a polyisocyanate component is 3 to 30 weight% is compoundable. When the amount of the polyisocyanate component used exceeds 30% by weight, the charge amount is lowered, which is not preferable. If the amount of the polyisocyanate component used is less than 3% by weight, it is difficult to ensure the necessary molecular weight, which is not preferable.
In the amorphous polyester resin forming step, a catalyst is used. The catalyst used for forming the first polyester resin contains one or more elements selected from sulfur element and fluorine element including at least sulfur element. The catalyst may be one type of compound or a mixture of two or more types of compounds. A strong acid compound is mentioned as a catalyst containing 1 or more types of elements selected from a sulfur element and a fluorine element including at least sulfur element. Specifically, p-toluenesulfonic acid monohydrate, bis (1,1,2,2,3,3,4,4,4-nonafluoro-1-butanesulfonyl) imide, scandium (III) triflate, Examples include dodecylbenzenesulfonic acid and sulfuric acid. The amount of the catalyst used is appropriately determined in consideration of the above-described content ranges of the sulfur element and the fluorine element. Specifically, the amount of the catalyst used is 0.1 to 2.0% by weight, preferably 0.2 to 1.0% by weight, based on the entire raw material used for forming the first polyester resin. . When the usage-amount of a catalyst is 0.1 to 2.0 weight%, content of a sulfur element and a fluorine element can be made into the range mentioned above. When the amount of the catalyst used exceeds 2.0% by weight, the resin is colored due to the progress of side reactions, which is not preferable. If the catalyst content is less than 0.1% by weight, it is difficult to ensure the molecular weight of the polyester resin.

The amorphous polyester-based resin synthesis step includes, for example, a first case where a first esterification step, a urethane extension step, a second esterification step, and a recovery step are performed, and a first esterification step. And a second case in which a second esterification step, a urethane extension step, and a recovery step are performed.
Hereinafter, the amorphous polyester-based resin synthesis step will be described for each step separately for the first case and the second case.

[First case]
<First esterification step>
In the first esterification step, first, a first polycarboxylic acid component, a polyol component, and a catalyst are placed in a reaction vessel.

In the first esterification step, after that, the inside of the reaction vessel is put under an inert gas atmosphere, and the mixture of the first polycarboxylic acid component, the polyol component, and the catalyst is heated and dissolved, and the first polycarboxylic acid component And a polyol component and a catalyst are formed.
The heating temperature for dissolving the mixture is appropriately determined in consideration of the type and amount of the first polycarboxylic acid component and polyol component used as the monomer.

In the first esterification step, the mixed solution is then heated to a predetermined temperature of 150 ° C. or lower. This temperature is the synthesis temperature of the polyester resin. Thereafter, the inside of the reaction vessel is evacuated, and the first polycarboxylic acid component and the polyol component are subjected to a dehydration condensation reaction at a synthesis temperature of the polyester resin for a predetermined time to form a polyester resin.
The synthesis temperature of the polyester resin can be lowered by adjusting the type and blending ratio of the monomers and further adjusting the type of the catalyst. As described above, the synthesis temperature of the polyester resin is 150 ° C. or lower, and preferably 80 to 150 ° C. When the synthesis temperature is 150 ° C. or lower, it is possible to suppress energy consumption during synthesis of the polyester resin. When the synthesis temperature exceeds 150 ° C., the energy consumption during synthesis of the polyester resin increases, which is not preferable. When the synthesis temperature is less than 80 ° C., the synthesis time of the polyester resin becomes long, which is not preferable.
The synthesis time of the polyester resin is appropriately determined in consideration of the synthesis temperature, the types and blending ratios of the polycarboxylic acid component and the polyol component used as monomers.

<Urethane extension process>
In the urethane elongation step, first, after returning the reaction vessel to normal pressure, the polyisocyanate component and the organic solvent are added to the solution in which the polyester resin is formed.
The organic solvent is added to reduce the viscosity of the mixed solution in the reaction vessel. Examples of the organic solvent that can be used in the urethane elongation step include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and ethyl acetate. The addition amount of the organic solvent is appropriately determined in consideration of the viscosity of the mixed solution in the reaction vessel.

In the urethane stretching step, the inside of the reaction vessel is then placed in an inert gas atmosphere, the polyester resin and the polyisocyanate component are reacted at a predetermined temperature for a predetermined time, and the polyester resin is expanded in urethane.
The reaction temperature for elongating the polyester resin with urethane is appropriately determined in consideration of the reaction time necessary for securing physical properties. Specifically, the reaction temperature is 60 to 100 ° C, and preferably 80 to 100 ° C. When the reaction temperature is 60 to 100 ° C., necessary physical properties can be secured while suppressing energy consumption. If the reaction temperature exceeds 100 ° C, the energy consumption increases, which is not preferable. When the reaction temperature is lower than 60 ° C., the reaction time for securing necessary physical properties becomes long, which is not preferable.
The reaction time for extending the polyester resin with urethane is appropriately determined in consideration of the reaction temperature, the types and blending ratios of the polycarboxylic acid component and the polyol component used as monomers.

<Second esterification step>
In the second esterification step, first, the second polycarboxylic acid component is added to the solution in which the urethane-extended polyester resin is formed.

  In the second esterification step, the second polycarboxylic acid component and the urethane-extended polyester resin are then subjected to a dehydration condensation reaction for a predetermined time at the synthesis temperature of the polyester resin under an inert gas atmosphere. The first polyester resin is formed by stretching with the polycarboxylic acid component.

<Recovery process>
In the recovery step, the organic solvent used in the urethane extension step is removed from the solution in which the first polyester resin is formed, thereby obtaining the first polyester resin.
As a method for removing the organic solvent, an evaporation method may be mentioned.

The obtained first polyester resin is an amorphous polyester resin and has the following characteristics (1) to (4).
(1) The aromatic ring concentration is 4.5 to 5.8 mol / kg.
(2) A weight average molecular weight (Mw) is 7000-50000.
(3) Glass transition temperature (Tg) is 50-70 degreeC.
(4) When the weight average molecular weight (Mw) is 7000 or more and less than 14,000, the expression 1 is satisfied, and when the weight average molecular weight (Mw) is 14000 or more and 50000 or less, the expression 2 is satisfied.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

[Second case]
<First esterification step>
As in the first case, the first esterification step is performed.

<Second esterification step>
In the second esterification step, first, after returning the reaction vessel to normal pressure, the second polycarboxylic acid component is added to the solution in which the polyester resin is formed.

  In the second esterification step, the inside of the reaction vessel is then placed in an inert gas atmosphere, and the second polycarboxylic acid component and the polyester resin are subjected to a dehydration condensation reaction for a predetermined time at the synthesis temperature of the polyester resin. It is elongated by the polycarboxylic acid component.

<Urethane extension process>
In the urethane stretching step, first, a polyisocyanate component and an organic solvent are added to a solution in which a polyester resin stretched by the second polycarboxylic acid component is formed.
The organic solvent is added to reduce the viscosity of the mixed solution in the reaction vessel. Examples of the organic solvent that can be used in the urethane elongation step include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and ethyl acetate. The addition amount of the organic solvent is appropriately determined in consideration of the viscosity of the mixed solution in the reaction vessel.

In the urethane stretching step, the polyester resin stretched with the second polycarboxylic acid component is reacted with the polyisocyanate component for a predetermined time at a predetermined temperature in an inert gas atmosphere, thereby extending the urethane. A polyester resin is formed.
The reaction temperature for extending the urethane of the polyester resin extended by the second polycarboxylic acid component is appropriately determined in consideration of the reaction time necessary for securing the physical properties. Specifically, the reaction temperature is 60 to 100 ° C, and preferably 80 to 100 ° C. When the reaction temperature is 60 to 100 ° C., necessary physical properties can be secured while suppressing energy consumption. If the reaction temperature exceeds 100 ° C, the energy consumption increases, which is not preferable. When the reaction temperature is lower than 60 ° C., the reaction time for securing necessary physical properties becomes long, which is not preferable.
The reaction time for urethane extension of the polyester resin extended by the second polycarboxylic acid component is the reaction temperature, the first polycarboxylic acid component used as a monomer, the second polycarboxylic acid component, and the polyol component. It is determined as appropriate in consideration of the type and mixing ratio.

<Recovery process>
In the recovery step, the organic solvent used in the urethane extension step is removed from the solution in which the first polyester resin is formed, thereby obtaining the first polyester resin.
As a method for removing the organic solvent, an evaporation method may be mentioned.

The obtained first polyester resin is an amorphous polyester resin and has the following characteristics (1) to (4).
(1) The aromatic ring concentration is 4.5 to 5.8 mol / kg.
(2) A weight average molecular weight (Mw) is 7000-50000.
(3) Glass transition temperature (Tg) is 50-70 degreeC.
(4) When the weight average molecular weight (Mw) is 7000 or more and less than 14,000, the expression 1 is satisfied, and when the weight average molecular weight (Mw) is 14000 or more and 50000 or less, the expression 2 is satisfied.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

2. Amorphous polyester resin latex forming step This amorphous polyester resin latex forming step is a step of forming a first polyester resin latex containing a first polyester resin which is an amorphous polyester resin.

In the amorphous polyester resin latex forming step, first, a first polyester resin and an organic solvent are put in a reaction vessel, and the first polyester resin is dissolved in the organic solvent. In the case where a mixture of two or more kinds of polyester resins having the above-mentioned characteristics (1) to (4) is used as the first polyester resin, the above-described characteristics (1) are used as the first polyester resin in this step. ) To (4), two or more kinds of polyester resins are put in a reaction vessel.
The content of the first polyester resin in the solution containing the first polyester resin is appropriately determined in consideration of the viscosity and the like.
Examples of the organic solvent that can be used in the amorphous polyester resin latex forming step include methyl ethyl ketone, isopropyl alcohol, ethyl acetate, and a mixed solvent thereof.

In the amorphous polyester resin latex forming step, the alkaline solution is gradually added while stirring the solution containing the first polyester resin, and water is further added at a predetermined rate to form an emulsion. .
The alkaline solution is added to neutralize the solution containing the first polyester resin. Examples of the alkaline solution that can be used in the amorphous polyester resin latex forming step include an aqueous ammonia solution and an amine compound. The addition amount of the alkaline solution is appropriately determined in consideration of the acidity of the solution containing the first polyester resin.
The amount of water added is appropriately determined in consideration of the particle size of the resulting latex. The rate of water addition is appropriately determined in consideration of the particle size distribution of the latex.

In the amorphous polyester resin latex forming step, thereafter, the organic solvent is removed from the emulsion until the first polyester resin, which is a solid content, has a predetermined concentration, and the first polyester containing the first polyester resin is obtained. A resin latex is obtained.
A method for removing the organic solvent includes a vacuum distillation method.
The concentration of the first polyester resin in the first sex polyester resin latex is appropriately determined in consideration of the latex viscosity, storage stability, economy, and the like. Specifically, the concentration of the first polyester resin is 10 to 50% by weight, preferably 20 to 40% by weight.

3. Crystalline polyester resin synthesis step This crystalline polyester resin synthesis step synthesizes a crystalline second polyester resin by dehydrating and condensing a polycarboxylic acid component and a polyol component at a temperature of 100 ° C or lower in the presence of a catalyst. It is a process to do.

In the crystalline polyester resin synthesis step, first, a polycarboxylic acid component, a polyol component, and a catalyst are placed in a reaction vessel.
Examples of the polycarboxylic acid component that can be used for the synthesis of the second polyester resin include aliphatic polycarboxylic acids as described above. Specific examples include adipic acid, sebacic acid, decanedioic acid, dodecanedioic acid and the like. Examples of the polyol component that can be used for the synthesis of the second polyester resin include aliphatic polyols as described above. Specific examples include 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and the like.
The catalyst used for the synthesis of the second polyester resin contains one or more elements selected from sulfur element and fluorine element including at least sulfur element. The catalyst may be one type of compound or a mixture of two or more types of compounds. As described above, as a catalyst containing at least one element selected from elemental sulfur and elemental fluorine including elemental sulfur, p-toluenesulfonic acid monohydrate, dodecylbenzenesulfonic acid, bis (1,1 , 2,2,3,3,4,4,4-nonafluoro-1-butanesulfonyl) imide, scandium (III) triflate and the like.

  In the crystalline polyester resin synthesis step, the inside of the reaction vessel is then placed in an inert gas atmosphere, and the mixture of the polycarboxylic acid component, the polyol component, and the catalyst is heated and dissolved, and the polycarboxylic acid component, the polyol component, and the catalyst are mixed. To form a mixed solution.

  In the crystalline polyester resin synthesis step, the mixed solution is then heated to a predetermined temperature of 100 ° C. or lower. This temperature is the synthesis temperature of the polyester resin. Thereafter, the inside of the reaction vessel is evacuated, and a polycarboxylic acid component and a polyol component are subjected to a dehydration condensation reaction at a polyester resin synthesis temperature for a predetermined time to form a second polyester resin.

The obtained second polyester resin is a crystalline polyester resin and has the following characteristics (A) to (E).
(A) The endothermic amount at the time of melting by differential scanning calorimetry is 2.0 to 10.0 W / g.
(B) The weight average molecular weight is 5000-15000.
(C) In the endothermic curve in differential scanning calorimetry, the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature is 3 to 5 ° C.
(D) It contains one or more elements selected from sulfur element and fluorine element including at least sulfur element.
(E) The content of the weight average molecular weight of 1000 or less is 1 to less than 10%.

4). Crystalline polyester resin latex formation process This crystalline polyester resin latex formation process is a process of forming the 2nd polyester resin latex containing the 2nd polyester resin which is a crystalline polyester resin.

In the crystalline polyester resin latex forming step, first, a second polyester resin and an organic solvent are placed in a reaction vessel, and the second polyester resin is dissolved in the organic solvent.
The content of the second polyester resin in the solution containing the second polyester resin is appropriately determined in consideration of the latex viscosity, storage stability, economy, and the like.
Examples of the organic solvent that can be used in the crystalline polyester resin latex forming step include methyl ethyl ketone, isopropyl alcohol, ethyl acetate, and a mixed solvent thereof.

In the crystalline polyester resin latex forming step, an alkaline solution is gradually added while stirring the solution containing the second polyester resin, and water is further added at a predetermined rate to form an emulsion.
The alkaline solution is added to neutralize the solution containing the second polyester resin. Examples of the alkaline solution that can be used in the crystalline polyester resin latex forming step include an aqueous ammonia solution and an amine compound. The addition amount of the alkaline solution is appropriately determined in consideration of the acidity of the solution containing the second polyester resin.
The amount of water added is appropriately determined in consideration of the particle size of the resulting latex. The rate of water addition is appropriately determined in consideration of the particle size distribution of the latex.

In the crystalline polyester resin latex forming step, after that, the organic solvent is removed from the emulsion until the second polyester resin, which is a solid content, has a predetermined concentration, and the second polyester resin latex containing the second polyester resin is obtained. Get.
A method for removing the organic solvent includes a vacuum distillation method.
The concentration of the second polyester resin in the second polyester resin latex is appropriately determined in consideration of storage stability, economy, and the like. Specifically, the concentration of the second polyester resin is 10 to 50% by weight, and preferably 20 to 40% by weight.

5. Liquid mixture forming step The liquid mixture forming step includes a first polyester resin latex, a second polyester resin latex, a colorant dispersion containing a colorant as necessary, and a mold release agent as necessary. In this step, the dispersion is mixed to form a mixture.

The mixed liquid forming step undergoes a colorant dispersion forming step, a release agent dispersion forming step, and a mixing step as necessary.
Hereinafter, the mixed liquid forming step will be described for each step.

<Colorant dispersion forming process>
In the colorant dispersion forming step, first, a colorant, an anionic surfactant, and a dispersion medium are placed in a reaction vessel.
As the colorant that can be used in the electrostatic image developing toner of this embodiment, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G , G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR ), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cadmium Mummer Curry Red, Antimony Zhu, Permanent Red 4R, Para Red, Phi-Sa Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake , Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue , Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid Examples include lean lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon, and mixtures thereof. The content of the colorant in the mixture of the colorant, the anionic surfactant and the dispersion medium is appropriately determined in consideration of the dispersion state and the like.
Examples of the anionic surfactant that can be used in the colorant dispersion forming step include alkylbenzene sulfonate. The content of the anionic surfactant in the mixture of the colorant, the anionic surfactant and the dispersion medium is appropriately determined in consideration of the dispersion state of the colorant.
Examples of the dispersion medium that can be used in the colorant dispersion forming step include glass beads. The content of the dispersion medium in the mixture of the colorant, the anionic surfactant, and the dispersion medium is appropriately determined in consideration of the dispersion state and dispersion time of the colorant.

In the colorant dispersion forming step, thereafter, a mixture of the colorant, the anionic surfactant and the dispersion medium is subjected to dispersion treatment to obtain a colorant dispersion.
Examples of a method for dispersing the mixture include a method using a milling bath, a method using an ultrasonic disperser, and a method using a microfluidizer.

<Releasing agent dispersion forming process>
In the release agent dispersion forming step, first, a release agent, an anionic surfactant, and water are put into a reaction vessel.
As a release agent usable in the electrostatic image developing toner of this embodiment, solid paraffin wax, microwax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax And fatty acid ester waxes, partially saponified fatty acid ester waxes, silicone varnishes, higher alcohols, carnauba waxes, and the like. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. The content of the release agent in the mixture of the release agent, the anionic surfactant and water is appropriately determined in consideration of the dispersion state and the like.
Examples of the anionic surfactant that can be used in the release agent dispersion forming step include alkylbenzene sulfonate. The content of the anionic surfactant in the mixture of the release agent, the anionic surfactant and water is appropriately determined in consideration of the dispersion state and the like.
The content of water in the mixture of the release agent, the anionic surfactant and water is appropriately determined in consideration of the dispersion state, storage stability, economy and the like.

In the release agent dispersion forming step, thereafter, a mixture of the release agent, the anionic surfactant, and water is dispersed to obtain a release agent dispersion.
An example of a method for dispersing the mixture is a method using a homogenizer.

<Mixing process>
In the mixing step, first, a first polyester resin latex, a second polyester resin latex, and water are placed in a reaction vessel. Thereafter, while stirring the mixture of the first polyester resin latex, the second polyester resin latex and water, in the mixture, if necessary, a colorant dispersion, and if necessary, a release agent dispersion To form a mixed solution containing a first polyester resin latex, a second polyester resin latex, a colorant dispersion containing a colorant if necessary, and a release agent dispersion if necessary To do.
The input amount of the first polyester resin latex is appropriately determined in consideration of toner physical properties and the like.
The input amount of the second polyester resin latex is appropriately determined in consideration of the physical properties of the toner.
The amount of water input is appropriately determined in consideration of the viscosity and economics of the mixture.
The input amount of the colorant dispersion is appropriately determined in consideration of the toner coloring power and the like.
The input amount of the release agent dispersion is appropriately determined in consideration of the physical properties of the toner.

6). Primary agglomerated particle forming step In this primary agglomerated particle forming step, a flocculant is added to the mixed solution, and the first polyester resin, the second polyester resin, a colorant as necessary, and a mold release as necessary. It is a step of aggregating the agent to form primary aggregated particle particles.

In the primary aggregated particle forming step, first, a first polyester resin latex, a second polyester resin latex, water, a colorant dispersion as necessary, and a release agent dispersion as necessary are included. While stirring the mixed solution, the flocculant and the acidic solution are added to the solution.
Examples of the aggregating agent that can be used in the primary aggregating toner forming step include those containing an iron element and a silicon element. Examples of the aggregating agent containing iron element and silicon element include iron-based metal salts. Specific examples include polysilica iron and polyaluminum chloride.
The addition amount of the flocculant is appropriately determined in consideration of the range of the content of iron element and sulfur element described above. Specifically, the addition amount of the flocculant is 0.5 to 3.0% by weight, preferably 1.0 to 2.5% by weight, based on the entire raw material used for forming the first polyester resin. is there. When the addition amount of the flocculant is 0.5 to 3.0% by weight, the contents of iron element and sulfur element can be set in the above-described ranges. If the amount of the flocculant added exceeds 3.0% by weight, the toner physical properties become too high, which is not preferable. If the addition amount of the flocculant is less than 0.5% by weight, the toner structure formation is insufficient, which is not preferable.
The acidic solution is added to make the mixed solution acidic and promote the aggregation reaction. Examples of the acidic solution that can be used in the primary aggregation toner forming step include a nitric acid solution and a hydrochloric acid solution. The addition amount of the acidic solution is appropriately determined in consideration of the alkalinity of the mixed solution.

In the primary agglomerated particle forming step, the solution is heated at a predetermined temperature increase rate while the solution after the addition of the flocculant and the acidic solution is dispersed. At this time, the first polyester resin, the second polyester resin, the colorant as necessary, and the release agent as necessary agglomerate to form primary aggregated particles having a predetermined volume average particle diameter. Thus, a primary aggregated particle dispersion containing primary aggregated particles is obtained.
The volume average particle diameter of the obtained primary agglomerated particles can be controlled by adjusting the stirring speed during the dispersion treatment, the temperature rise temperature of the solution, the agglomeration reaction time, and the like. The volume average particle diameter of the primary agglomerated particles is appropriately determined in consideration of the toner particle diameter and the like. Specifically, the volume average particle diameter of the primary aggregated particles is preferably 2.5 to 8.5 μm, and more preferably 3.0 to 4.5 μm.
The temperature increase rate of the solution after the addition of the flocculant and the acidic solution is appropriately determined in consideration of the primary aggregate particle size and the like.
As a method for dispersing the solution after adding the flocculant and the acidic solution, a method using a homogenizer can be mentioned.

7). Coated aggregated particle forming step This coated aggregated particle forming step is a step of forming a coated aggregated particle by providing a coating layer formed of the first polyester resin on the surface of the primary aggregated particle.

In the coated aggregated particle forming step, first, while dispersing the primary aggregated particle dispersion containing the primary aggregated particles, the first polyester resin latex is added to the dispersion, and the primary aggregated particles and the first aggregate are added for a predetermined time. A polyester resin is agglomerated to provide a coating layer formed from the first polyester resin on the surface of the primary agglomerated particles. As a result, a coated aggregated particle dispersion containing coated aggregated particles having a coating layer on the outer surface is obtained.
The addition amount of the first polyester resin latex is appropriately determined in consideration of the physical properties of the toner.
The aggregation reaction time is appropriately determined in consideration of the toner particle diameter and the like.
An example of a method for dispersing the primary aggregated particle dispersion is a method using a homogenizer.

In the coated aggregated particle forming step, an alkaline solution is then added to the coated aggregated particle dispersion to adjust the pH and stop aggregation.
Examples of the alkaline solution that can be used for stopping the aggregation include an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution. The addition amount of the alkaline solution is appropriately determined in consideration of the acidity of the coated aggregated particle dispersion.

8). Fusion coalescence step This fusion coalescence step is a step of fusing and coalescing the coated aggregated particles at a temperature higher than the glass transition temperature of the first polyester resin.

In the coalescence and coalescence process, the particles in the coated aggregated particles are coalesced and coalesced by treatment for a predetermined time at a temperature higher than the glass transition temperature of the first polyester resin. As a result, toner particles having a predetermined volume average particle diameter having a coating layer on the outer surface are formed, and a toner particle dispersion containing toner particles is obtained.
The fusion reaction temperature is appropriately determined in consideration of toner physical properties, shape, economy, and the like. The fusion reaction time is appropriately determined in consideration of the toner shape and the like.

After the coalescence process, the toner particles are separated from the toner particle dispersion.
An example of a method for separating the toner particles from the toner particle dispersion is a filtration method.

The resulting toner particles have the following characteristics (1) to (6).
(1) It contains at least three elements selected from the group consisting of iron element, silicon element, sulfur element and fluorine element, including at least iron element, silicon element and sulfur element.
(2) The iron element content is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, the silicon element content is 1.0 × 10 ^{3 to} 5.0 × 10 ³ ppm, and sulfur. Elemental content is 500-3000 ppm. When elemental fluorine is included, the content of elemental fluorine is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm.
(3) Acid value is 3-25 mgKOH / g.
(4) The volume average particle diameter is 3 to 9 μm.
(5) The number of particles having a number average particle diameter of 3 μm or less is 3% by number or less.
(6) The ratio of the abundance of particles having a particle size of 3 μm or less to the abundance of particles having a number average particle size of 1 μm or less is 2.0 to 4.0.

C. Effect According to the electrostatic charge developing toner of this embodiment, at least three elements selected from the group consisting of iron element, silicon element, sulfur element and fluorine element, including at least iron element, silicon element and sulfur element The content of iron element is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, the content of silicon element is 1.0 × 10 ^{3 to} 5.0 × 10 ³ ppm, sulfur When the element content is 500 to 3000 ppm and the fluorine element is contained, the fluorine element content is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, and the binder resin is at least an amorphous polyester. The non-crystalline polyester-based resin includes (1) an aromatic ring concentration of 4.5 to 5.8 mol / kg, (2) a weight average molecular weight (Mw) of 7000 to 50000, and (3 ) Glass transition temperature (Tg) When the weight average molecular weight (Mw) is from 7000 to less than 14000, Formula 1 is satisfied, and when the weight average molecular weight (Mw) is from 14000 to 50000, Formula 2 is satisfied. For this reason, it is possible to obtain a toner for developing an electrostatic charge image that is excellent in low-temperature fixability and storage stability and can suppress energy consumption during toner production.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

Further, according to the method for producing a toner for developing an electrostatic charge image of this embodiment, the first carboxylic acid component and the polyol component are subjected to dehydration condensation at a temperature of 150 ° C. or less in the presence of a catalyst, and (i) dehydration The resin obtained by the condensation is urethane-extended in the presence of a polyisocyanate component, and then is extended by a second polycarboxylic acid component having a substituent corresponding to three or more carboxyl groups, and the first polyester resin Or (ii) extending the resin obtained by dehydration condensation with a second polycarboxylic acid component having a substituent corresponding to three or more carboxyl groups, and then in the presence of a polyisocyanate component. Elongate urethane to synthesize amorphous polyester resin, form amorphous polyester resin synthesis process, and form latex of amorphous polyester resin Crystalline polyester resin synthesis in which a crystalline polyester resin latex is formed, and an aliphatic polycarboxylic acid component and an aliphatic polyol component are dehydrated and condensed at a temperature of 100 ° C. or lower in the presence of a catalyst. A step of forming a latex of a crystalline polyester resin, a step of forming a crystalline polyester resin latex, and a step of forming a mixture by mixing at least an amorphous polyester-based resin latex and a crystalline polyester resin latex Adding a flocculant to the mixed liquid, aggregating the amorphous polyester resin and the crystalline polyester resin to form primary agglomerated particles, and forming a primary agglomerated particle on the surface of the primary agglomerated particles. Coated agglomerated particles that are provided with a coating layer formed from a conductive polyester resin to form coated agglomerated particles And a coalescing and coalescing step in which the coated aggregated particles are coalesced and coalesced at a temperature higher than the glass transition temperature of the amorphous polyester resin. The amorphous polyester resin comprises (1) aromatic ring concentration Is 4.5 to 5.8 mol / kg, (2) the weight average molecular weight (Mw) is 7000 to 50000, (3) the glass transition temperature (Tg) is 50 to 70 ° C., and (4) the weight. When the average molecular weight (Mw) is 7000 or more and less than 14000, the formula 1 is satisfied, and when the weight average molecular weight (Mw) is 14,000 or more and 50000 or less, the formula 2 is satisfied. The endothermic amount at the time of melting is 2.0 to 10.0 W / g, (B) the weight average molecular weight is 5000 to 15000, and (C) the endothermic curve during endothermic measurement in differential scanning calorimetry. The difference between the start temperature and the endothermic peak temperature is 3 to 5 ° C., and (D) contains one or more elements selected from at least sulfur elements from sulfur elements and fluorine elements, and (E) a weight average molecular weight of 1000 or less The content of is less than 1 to less than 10%, the catalyst contains one or more elements selected from sulfur element and fluorine element including at least sulfur element, and the flocculant contains iron element and silicon element. Therefore, it is possible to produce a toner for developing an electrostatic charge image that is excellent in low-temperature fixability and storage stability and can suppress energy consumption during the production of the toner.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2

  Hereinafter, based on an Example and a comparative example, this invention is demonstrated more concretely. The following examples are merely examples of the present invention and do not limit the present invention.

  First, prior to description of Examples and Comparative Examples, various measurement methods and evaluation methods will be described.

<Aromatic ring concentration>
The aromatic ring concentration of the polyester resin was determined by analyzing the ultraviolet absorption spectrum. Specifically, an ultraviolet spectrum in a wavelength range of 220 to 340 nm was measured with a light transmittance visible ultraviolet spectrometer U-3410 (manufactured by Hitachi, Ltd.). Two points showing the minimum intensity located in the vicinity of 230 nm and 310 nm were connected and baselined. A perpendicular line was drawn from the maximum absorbance around 240 to 300 nm to the baseline, and the absorbance was determined from the length of the perpendicular line. Using a calibration curve prepared using a known concentration of phenol, the aromatic ring concentration was calculated from the obtained absorbance.

<Weight average molecular weight> and <Content of weight average molecular weight of 1000 or less>
The weight average molecular weight and the content of weight average molecular weight of 1000 or less were determined by gel permeation chromatography (GPC) measurement. Specifically, Waters e2695 (manufactured by Nippon Waters Co., Ltd.) was used as a measuring device, and Inertsil CN-3 25 cm double (manufactured by GL Sciences Inc.) was used as a column. Further, 30 mg of a polyester resin was added to 20 mL of tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.), stirred for 1 hour, and then filtered through a 0.2 μm filter. Tetrahydrofuran (THF) sample solution was injected into a measuring apparatus at 20 μL, and measurement was performed under the conditions of 40 ° C. and a flow rate of 1.0 mL / min.

<Glass transition temperature>
The glass transition temperature (° C.) of the polyester resin was determined from a differential scanning calorimetry curve obtained by a differential scanning calorimeter measurement specified in ASTM D3418-08. Specifically, using a differential scanning calorimeter Q2000 (manufactured by TA Instruments), the temperature is raised from room temperature to 150 ° C. at a rate of 10 ° C. per minute as the first temperature raising step. After holding at 150 ° C. for 1 minute, the temperature was lowered to 0 ° C. at a rate of 10 ° C. per minute using liquefied nitrogen. After holding at 0 ° C. for 5 minutes, the temperature was raised again from 0 ° C. to 150 ° C. at a rate of 10 ° C. per minute as the second temperature raising step, and the glass transition temperature was determined from the obtained differential scanning calorimetry curve.

<Endotherm during melting of crystalline polyester resin> and <Difference between endothermic start temperature and endothermic peak temperature during temperature rise>
The endothermic amount (W / g) at the time of melting of the crystalline polyester resin and the difference (° C.) between the endothermic start temperature and the endothermic peak temperature at the time of temperature rise were determined by differential scanning calorimetry (DSC) defined in ASTM D3418-08 It calculated | required from the obtained differential scanning calorific value curve. Specifically, using a differential scanning calorimeter Q2000 (manufactured by TA Instruments), the temperature is raised from room temperature to 150 ° C. at a rate of 10 ° C. per minute as the first temperature raising step. After maintaining at 150 ° C for 1 minute, the temperature was lowered to 0 ° C at a rate of 10 ° C per minute using liquefied nitrogen. After maintaining at 0 ° C. for 5 minutes, as the second temperature raising step, the temperature was raised again from 0 ° C. to 150 ° C. at a rate of 10 ° C. per minute. From the obtained differential scanning calorimetry curve, the crystalline polyester resin was melted. The endothermic amount and the difference between the endothermic start temperature during temperature rise and the endothermic peak temperature were determined.

<Element content>
The contents of iron element, silicon element, sulfur element and fluorine element were determined by fluorescent X-ray analysis. Specifically, fluorescent X-ray analyzer EDX-720 (manufactured by Shimadzu Corporation) was used as a measuring device, and measurement was performed under the conditions of an X-ray tube voltage of 50 kV and a sample molding amount of 30.0 g. Using the intensity (cps / μA) from the quantitative result derived by fluorescent X-ray measurement, the content of each element was determined.

<Acid value>
The acid value (mgKOH / g) is an acid value measuring method defined in JIS K 0070-1992 “Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. It was determined according to the neutralization titration method.

<Volume average particle diameter>
The volume average particle diameter was measured by a pore electrical resistance method. Specifically, a Coulter counter (manufactured by Beckman Coulter, Inc.) is used as a measuring device, ISOTON II (manufactured by Beckman Coulter, Inc.) is used as an electrolyte, and an aperture tube with an aperture diameter of 100 μm is used. It measured on condition of this. Based on the measured particle size distribution of the particles, the volume occupied by the particles included in the divided particle size range was accumulated from the smaller diameter side, and the particle diameter at 50% accumulation was defined as the volume average particle diameter Dv50.

<Abundance of particles with a particle size of 3 μm or less>
The abundance of particles having a particle size of 3 μm or less was measured by the pore electrical resistance method. Specifically, a Coulter counter (manufactured by Beckman Coulter, Inc.) is used as a measuring device, ISOTON II (manufactured by Beckman Coulter, Inc.) is used as an electrolyte, and an aperture tube with an aperture diameter of 100 μm is used. It measured on condition of this. Based on the measured particle size distribution, the number of particles having a particle size of 3 μm or less was defined as the abundance of particles having a particle size of 3 μm or less.

<Abundance of particles with particle size of 1 μm or less>
The abundance of particles having a particle size of 1 μm or less was measured by a dynamic light scattering method. Specifically, a nanotrack particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.) was used as the measuring device. Based on the measured particle size distribution, the number of particles having a particle size of 1 μm or less was defined as the abundance of particles having a particle size of 1 μm or less.

<Fixability evaluation>
Using a belt-type fixing device (color laser 660 model (product name) fixing device manufactured by Samsung Electronics Co., Ltd.), an unfixed image for testing with a 100% solid pattern was printed on 60 g paper (X-9 manufactured by Boise) The product was fixed on a test paper (product name)) under the conditions of a fixing speed of 160 mm / second and a fixing time of 0.08 seconds. Fixing of the unfixed test image was performed at 5 ° C. intervals in the range of 100 ° C. to 180 ° C.
The initial optical density (OD) of the fixed image was measured. Thereafter, 3M 810 tape was attached to the image area, and a 500 g weight was reciprocated five times, and then the tape was removed. Thereafter, the optical density (OD) after tape removal was measured.
The lowest temperature at which the fixability (%) obtained by the following formula was 90% or more was defined as the fixing temperature.
Fixability (%) = (initial optical density / optical density after removing tape) × 100

<Preservation evaluation>
After 100 g of toner was put into a mixer (KM-LS2K (trade name) manufactured by Daewha TECH), 0.5 g of NX-90 (manufactured by Nippon Aerosil Co., Ltd.) and RX-200 (Nippon Aerosil Co., Ltd.) were used as external additives. 1.0 g) and 0.5 g of SW-100 (Titanium Industry Co., Ltd.) were added. Thereafter, the external additive was adhered to the toner particles by stirring for 4 minutes at a stirring speed of 8000 rpm. Thereafter, the toner to which the external additive is attached is put into a developing machine (developing machine of color laser 660 model (trade name) manufactured by Samsung Electronics Co., Ltd.), and the temperature is 23 ° C. and the relative humidity is 55 using a constant temperature and humidity oven. After being stored for 2 hours in an environment of% (normal temperature and humidity), it was further stored for 48 hours in an environment of 40 ° C. and 90% relative humidity (high temperature and high humidity).
After storage under these conditions, the presence or absence of toner caking in the developing machine was visually observed, and a 100% solid pattern was output. The output image was visually observed, and the storage stability was evaluated as follows. .
○: Good image, no caking △: Poor image, no caking ×: Caking occurred

<Chargeability evaluation>
In a 60 ml glass container, 28.5 g of a magnetic carrier (model SY129 (trade name) manufactured by KDK) and 1.5 g of toner were put. Then, it stirred using the turbula mixer in the environment of temperature 23 degreeC and relative humidity 55% (normal temperature normal humidity). A charge saturation curve showing the relationship between the stirring time and the charge amount of the toner was prepared by measuring the charge amount of the toner by the electric field separation method at every predetermined stirring time, and the chargeability was evaluated as follows.
○: The charging saturation curve is smooth and the fluctuation range is small after saturation charging. Δ: The charging saturation curve jumps up slightly or after the saturation charging, the fluctuation range is slightly (maximum 30%). X: When the charge is not saturated or the fluctuation range is large after saturation charge (30% or more)

  Next, comparison of amorphous polyester resin latex containing amorphous polyester resin used in Examples 1 to 17 and comparative example of amorphous polyester resin latex containing amorphous polyester resin used in Examples Production Examples 1 to 13 will be described.

Production Example 1
<First esterification step>
A 500 ml separable flask equipped with a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer was added to a propylene oxide 2 mol adduct of bisphenol A, which is a polyol component Y 291.3 g of polyether BPX-11 (trade name), 67.1 g of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) as the first polycarboxylic acid component X1, and paratoluenesulfonic acid / water as a catalyst 2.7 g of a Japanese product (PTSA (abbreviation), manufactured by Wako Pure Chemical Industries, Ltd.) was added. Thereafter, nitrogen was introduced into the flask, and the mixture of bisphenol A propylene oxide 2-mol adduct, maleic anhydride and paratoluenesulfonic acid monohydrate was brought to 70 ° C. while stirring the flask with a stirrer. Dissolved by heating. Thereafter, the mixed solution in the flask was heated to 97 ° C. while stirring in the flask. Thereafter, the flask was evacuated (less than 10 mPa · s), and while stirring in the flask, a dehydration condensation reaction between maleic anhydride and propylene oxide 2 mol adduct of bisphenol A was performed at 97 ° C. for 45 hours to obtain a polyester resin. Formed.

<Urethane extension process>
After returning the inside of the flask to atmospheric pressure, 27.9 g of diphenylmethane diisocyanate (MDI (abbreviation), manufactured by Wako Pure Chemical Industries, Ltd.), which is a polyisocyanate component Z, and 40 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent are added to the flask. Added. Thereafter, nitrogen is introduced into the flask, and the polyester resin obtained in the first esterification step is reacted with diphenylmethane diisocyanate until the unreacted diphenylmethane diisocyanate disappears at a synthesis temperature of 97 ° C. while stirring the flask. To form a urethane-extended polyester resin. The absence of unreacted diphenylmethane diisocyanate was confirmed by removing a part of the solution from the flask, measuring the solution with an infrared spectrophotometer, and eliminating an isocyanate-derived peak in the vicinity of 2275 cm ⁻¹ .

<Second esterification step>
After the urethane stretched polyester resin was formed, pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.9, which is the second polycarboxylic acid component X2, was added to the flask. Thereafter, nitrogen was introduced into the flask, and while stirring in the flask, pyromellitic anhydride and urethane-extended polyester resin were subjected to a dehydration condensation reaction at a synthesis temperature of 97 ° C. for 30 hours. The polyester resin containing the repeating unit represented by this was formed.

<Recovery process>
Amorphous polyester resin P1 was obtained by evaporating toluene from the solution in which the polyester resin obtained in the second esterification step was formed.

  The obtained amorphous polyester resin P1 has an aromatic ring concentration of 4.6 mol / kg, a content of the repeating unit represented by the general formula (2) of 0.12 mol / kg, and a weight average molecular weight. 16000, the glass transition temperature was 57 ° C., and the acid value was 14 mgKOH / g.

<Latex formation process (emulsification process)>
Into a 3 liter double jacket reaction vessel, 300 g of amorphous polyester resin P1, 250 g of methyl ethyl ketone (MEK (abbreviation)), and 50 g of isopropyl alcohol (IPA (abbreviation)) were charged. Thereafter, the amorphous polyester resin P1 was dissolved in a mixed solvent of methyl ethyl ketone and isopropyl alcohol while stirring the reaction vessel with a half-moon type impeller in an environment of about 30 ° C. Thereafter, 26 g of 5% aqueous ammonia solution was gradually added to the reaction vessel while stirring the reaction vessel, and then 1200 g of water was added at a rate of 20 g / min to form an emulsion. Thereafter, the mixed solvent of methyl ethyl ketone and isopropyl alcohol is removed from the emulsion by a vacuum distillation method until the concentration of the amorphous polyester resin P1 which is a solid content becomes 20% by weight, and the amorphous polyester resin latex is obtained. L1 was obtained.

Production Examples 2-14.
In Production Examples 2 to 14, non-crystalline polyester resins P2 to P14 were synthesized by synthesizing amorphous polyester resins P2 to P14 in the same manner as Production Example 1 except that the production conditions were changed as shown in Table 1. Amorphous polyester resin latexes L2 to L14 containing P14 were obtained.
However, in Production Examples 12 and 13, the synthesis time after the addition of the first polycarboxylic acid component X1 was 2 hours. In Production Example 14, after the first esterification step, the second polycarboxylic acid component X2 was added to perform the second esterification step, and then the urethane elongation step and the recovery step were performed.

  Table 1 shows the production conditions and physical properties of the amorphous polyester resins P1 to P14 obtained in Production Examples 1 to 17. Table 1 shows the production conditions for the amorphous polyester resin latexes L1 to L14 including the amorphous polyester resins P1 to P14.

なお、表１中、「ＢＰＥ−２０」はビスフェノールＡのエチレンオキサイド２モル付加物（三洋化成工業社製のニューポールＢＰＥ−２０（商品名））を示し、「ＥＧ」はエチレングリコールを示し、「Ｎｆ２ＮＨ」は（１，１，２，２，３，３，４，４，４−ノナフルオロ−１−ブタンスルホニル）イミド（和光純薬社製）を示す。

In Table 1, “BPE-20” represents an adduct of bisphenol A with ethylene oxide 2 mol (Newpol BPE-20 (trade name) manufactured by Sanyo Chemical Industries), “EG” represents ethylene glycol, “Nf2NH” represents (1,1,2,2,3,3,4,4,4-nonafluoro-1-butanesulfonyl) imide (manufactured by Wako Pure Chemical Industries, Ltd.).

Comparative production examples 1-13.
In Comparative Production Examples 1 to 13, the amorphous polyester resins Q1 to Q13 were synthesized in the same manner as in Production Example 1 except that the production conditions were changed as shown in Table 2, and the amorphous polyester resin Q1 was synthesized. Amorphous polyester resin latexes F1 to F13 containing -Q13 were obtained.
However, in Comparative Production Examples 9 to 12, the synthesis time after the addition of the first polycarboxylic acid component X1 was 2 hours. In Comparative Production Examples 1 to 3 and 7, since the second polycarboxylic acid component X2 was not used, the second esterification step was not performed, and the recovery step was performed after the urethane extension step.

  Table 2 shows the production conditions and physical properties of the amorphous polyester resins Q1 to Q13 obtained in Comparative Production Examples 1 to 13. Table 2 shows the production conditions for the amorphous polyester resin latexes F1 to F13 including the amorphous polyester resins Q1 to Q13.

なお、表２中、「ＢＰＥ−２０」はビスフェノールＡのエチレンオキサイド２モル付加物（三洋化成工業社製のニューポールＢＰＥ−２０（商品名））を示し、「ＥＧ」はエチレングリコールを示す。

In Table 2, “BPE-20” represents a 2-mol adduct of bisphenol A with ethylene oxide (Newpol BPE-20 (trade name) manufactured by Sanyo Chemical Industries), and “EG” represents ethylene glycol.

  Next, Production Example 15 of an amorphous polyester resin latex containing two types of amorphous polyester resins used in the examples will be described.

Production Example 15.
In a 3 liter double jacket reaction vessel, 150 g of amorphous polyester resin P1, 150 g of amorphous polyester resin P2, 250 g of methyl ethyl ketone (MEK (abbreviation)), 50 g of isopropyl alcohol (IPA (abbreviation)), Was introduced. Thereafter, the amorphous polyester resins P1 and P2 were dissolved in a mixed solvent of methyl ethyl ketone and isopropyl alcohol while stirring in the reaction vessel using a half-moon type impeller in an environment of about 30 ° C. Thereafter, 27 g of 5% aqueous ammonia solution was gradually added to the reaction vessel while stirring in the reaction vessel, and then 1200 g of water was added at a rate of 20 g / min to form an emulsion. Thereafter, the mixed solvent of methyl ethyl ketone and isopropyl alcohol is removed from the emulsified liquid by a vacuum distillation method until the concentration of the amorphous polyester resins P1 and P2 which are solids is 20% by weight. Resin latex L15 was obtained.

  Next, a production example of a crystalline polyester resin latex containing a crystalline polyester resin used in Examples and Comparative Examples will be described.

Production Example 16.
In a 500 ml separable flask, 198.8 g of 1,9-nonanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 250.8 g of dodecanedioic acid (manufactured by Wako Pure Chemical Industries, Ltd.), paratoluenesulfonic acid monohydrate ( 0.45 g of PTSA (abbreviation), manufactured by Wako Pure Chemical Industries, Ltd. was added. Thereafter, nitrogen was introduced into the flask, and the mixture of 1,9-nonanediol, dodecanedioic acid and paratoluenesulfonic acid monohydrate was heated to 80 ° C. while stirring the flask with a stirrer. Dissolved. Thereafter, the mixed solution in the flask was heated to 97 ° C. while stirring in the flask. Thereafter, the inside of the flask was evacuated (10 mPa · s or less), and while the inside of the flask was stirred, a dehydration condensation reaction between 1,9-nonanediol and dodecanedioic acid was performed at 97 ° C. for 5 hours to obtain a crystalline polyester resin P16. Got.

  This crystalline polyester resin P16 had a weight average molecular weight of 6000 and a content of weight average molecular weight of 1000 or less was 7.2%. Further, the melting point (endothermic peak temperature) in the differential scanning calorimeter is 70.1 ° C., and in the differential scanning calorimetry curve, the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature is 4.3 ° C. The endothermic amount was 3.4 W / g. Moreover, the acid value was 9.20 mgKOH / g and the sulfur content was 186.62 ppm.

  Thereafter, 300 g of crystalline polyester resin P16, 250 g of methyl ethyl ketone (MEK (abbreviation)) and 50 g of isopropyl alcohol (IPA (abbreviation)) were charged into a 3 liter double jacket reaction vessel. Thereafter, in an environment of about 30 ° C., the crystalline polyester resin P16 was dissolved in a mixed solvent of methyl ethyl ketone and isopropyl alcohol while stirring the inside of the reaction vessel using a half-moon type impeller. Thereafter, 25 g of 5% aqueous ammonia solution was gradually added to the reaction vessel while stirring in the reaction vessel, and then 1200 g of water was added at a rate of 20 g / min to form an emulsion. Thereafter, the mixed solvent of methyl ethyl ketone and isopropyl alcohol was removed from the emulsified liquid by a vacuum distillation method until the concentration of the crystalline polyester resin P16 as a solid content was 20% by weight, to obtain a crystalline polyester resin latex L16. .

Production Examples 17-18.
In Production Examples 17 to 18, except that production conditions were changed as shown in Table 3, crystalline polyester resins P17 to P18 were synthesized in the same manner as Production Example 16 to obtain crystalline polyester resin latexes L17 to L18. It was.

  Table 3 shows production conditions and physical properties of the crystalline polyester resins P16 to P18 obtained in Production Examples 16 to 18.

なお、表３中、「１．９−ＮＤ」は１,９−ノナンジオールの投入量を示し、「ＤＤＡ」はドデカン二酸の投入量を示し、「ＰＴＳＡ」はパラトルエンスルホン酸・１水和物の投入量を示し、「Ｎｆ２ＮＨ」はビス（１，１，２，２，３，３，４，４，４−ノナフルオロ−１−ブタンスルホニル）イミドの投入量を示し、「ＴＢＴ」はテトラ−ｎ−ブトキシチタンの投入量を示す。また、表２中、「Ｍｗ」は重量平均分子量を示し、「１０００以下含有率」は重量平均分子量１０００以下の含有率を示す。また、「吸熱ピーク−吸熱開始」は昇温時吸熱開始温度と吸熱ピーク温度の差を示す。また、「ＡＶ」は酸価を示し、「Ｓ」は硫黄元素の含有量を示し、「Ｆ」はフッ素元素の含有量を示す。

In Table 3, “1.9-ND” indicates the input amount of 1,9-nonanediol, “DDA” indicates the input amount of dodecanedioic acid, and “PTSA” indicates p-toluenesulfonic acid · 1 water. “Nf2NH” indicates the input amount of bis (1,1,2,2,3,3,4,4,4-nonafluoro-1-butanesulfonyl) imide, and “TBT” indicates The input amount of tetra-n-butoxy titanium is shown. In Table 2, “Mw” represents a weight average molecular weight, and “1000 or less content” represents a content having a weight average molecular weight of 1000 or less. "Endothermic peak-endothermic start" indicates the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature. “AV” indicates the acid value, “S” indicates the content of sulfur element, and “F” indicates the content of fluorine element.

  Next, Production Example 19 of a colorant dispersion containing a colorant used in Examples and Comparative Examples will be described.

Production Example 19.
In a milling bath, put 60 g of cyan pigment (PB 15: 3 (C.I. No.)) and 10 g of an anionic reactive surfactant (HS-10 (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 400 g of glass beads having a diameter of 0.8 to 1 mm were introduced. Thereafter, the inside of the milling bath was milled at room temperature to obtain a colorant dispersion.

  Next, Production Example 20 of a release agent dispersion containing a release agent used in Examples and Comparative Examples will be described.

Production Example 20.
In a reaction vessel, 270 g of paraffin wax (HNP-9 (trade name) manufactured by Nippon Seiwa Co., Ltd.), 2.7 g of an anionic surfactant (Dowfax2A1 (trade name) manufactured by Dow Chemical Company), and 400 g of ion-exchanged water And put it in. Thereafter, the inside of the reaction vessel was heated to 110 ° C. and dispersed using a homogenizer (Ultra Turrax T50 (trade name) manufactured by IKA). Product name)) to obtain a release agent dispersion.

  Next, a method for producing toners for developing an electrostatic charge image in Examples and Comparative Examples will be described.

Example 1.
Into a 3 liter reaction vessel, 600 g of amorphous polyester resin latex L1 which is a resin latex for forming a core, 100 g of crystalline polyester resin latex L16 which is a resin latex for forming a core, and 560 g of deionized water are charged. did. Thereafter, 70 g of the colorant dispersion obtained in Production Example 19 and 80 g of the release agent dispersion obtained in Production Example 20 were added to the reaction vessel while stirring in the reaction vessel, and the concentration was further reduced to 0. 30 g of 3N nitric acid and 25 g of polysilica iron PSI-100 (manufactured by Seiko Co., Ltd.) were added. Then, while stirring the inside of the reaction vessel using a homogenizer (Ultra Turrax T50 (trade name) manufactured by IKA), the temperature of the mixed solution in the flask was increased to 50 ° C. at a rate of 1 ° C./min. Until the amorphous polyester resin P1, the crystalline polyester resin P16, the colorant, and the release agent are aggregated to obtain primary aggregated particles having a predetermined volume average particle diameter, the temperature increases at a rate of 0.03 ° C./min. The mixture was warmed to form primary aggregated particles having a volume average particle diameter of 5.2 μm. It was confirmed by taking out a part of the mixed solution from the reaction vessel and analyzing the primary aggregated particles contained in the solution that the primary aggregated particles had a predetermined volume average particle diameter.
Thereafter, while stirring the inside of the reaction vessel, 300 g of amorphous polyester resin latex L1 which is a latex for forming a shell is added to the reaction vessel, and the primary aggregated particles and the amorphous polyester resin P1 are added for 30 minutes. And a coating layer made of an amorphous polyester resin P1 was formed on the outer surface of the primary aggregated particles to obtain coated aggregated particles. Thereafter, an aqueous sodium hydroxide solution having a concentration of 0.1 N was added to the reaction vessel, and the pH of the mixed solution in the reaction vessel was adjusted to 9.5. After 20 minutes, the temperature of the mixed solution in the reaction vessel was increased to 83 ° C., and the particles in the coated aggregated particles were fused and united for 2 hours to form toner particles having a coating layer on the outer surface.
Thereafter, the mixed solution in the reaction vessel was cooled to 28 ° C. or lower, and then filtered to collect toner particles, followed by drying to obtain an electrostatic charge image developing toner 1.

The obtained electrostatic charge image developing toner 1 had a sulfur element content of 945 ppm, an iron element content of 2212 ppm, and a silicon element content of 2212 ppm. The acid value was 12 mgKOH / g. The volume average particle size is 5.8 μm, the abundance of particles having a particle size of 3 μm or less is 1.9% by number, the abundance of particles having a particle size of 1 μm or less is 0.5% by number, The ratio of the abundance of particles having a particle diameter of 3 μm or less to the abundance of particles having a diameter of 1 μm or less was 3.8.
The obtained toner 1 for developing an electrostatic image has a fixing temperature of 120 ° C., a storability evaluation of “good”, and a chargeability evaluation of “good”. Moreover, the thickness of the coating layer was 0.3 μm.

Examples 2-17 and Comparative Examples 1-13.
In Examples 2 to 17 and Comparative Examples 1 to 13, toners 2 to 30 for developing electrostatic images were obtained in the same manner as in Example 1 except that the production conditions were changed as shown in Tables 4 and 5. .
However, in Example 4 and Comparative Examples 6 to 9, crystalline polyester resin latex was not used as the resin latex for forming the core.
In Examples 2 to 17 and Comparative Examples 1 to 13, the volume average particle size of the primary aggregated particles was a value between 4 and 5 μm. Further, the pH of the mixed solution at the time of the fusion reaction when forming the toner particles is a value between 7.5 and 9.0, the fusion reaction temperature is a temperature between 80 and 90 ° C., and the fusion reaction time. Was between 3 and 5 hours. Moreover, the thickness of the coating layer was a value between 0.2-1 μm.

  Tables 4 and 5 show the production conditions and physical properties of the electrostatic image developing toners 1 to 30 of Examples 1 to 17 and Comparative Examples 1 to 13.

なお、表４中、上段において、「ワックス分散液」は一次凝集粒子の形成時に用いたワックス分散液中のワックスの種類を示し、「シアン顔料分散液」は一次凝集粒子の形成時に用いた着色剤分散液中のアニオン性反応性界面活性剤の種類を示し、「ＰＳＩ」は一次凝集粒子の形成時に用いた凝集剤の種類を示す。

In Table 4, in the upper part, “wax dispersion” indicates the type of wax in the wax dispersion used in forming the primary aggregated particles, and “cyan pigment dispersion” indicates the color used in forming the primary aggregated particles. The type of anionic reactive surfactant in the agent dispersion is shown, and “PSI” shows the type of flocculant used when forming the primary aggregated particles.

なお、表５中、上段において、「ワックス分散液」は一次凝集粒子の形成時に用いたワックス分散液中のワックスの種類を示し、「シアン顔料分散液」は一次凝集粒子の形成時に用いた着色剤分散液中のアニオン性反応性界面活性剤の種類を示し、「ＰＳＩ」は一次凝集粒子の形成時に用いた凝集剤の種類を示す。

In Table 5, in the upper part, “wax dispersion” indicates the type of wax in the wax dispersion used when forming the primary aggregated particles, and “cyan pigment dispersion” is the color used when forming the primary aggregated particles. The type of anionic reactive surfactant in the agent dispersion is shown, and “PSI” shows the type of flocculant used when forming the primary aggregated particles.

  As shown in Table 4, the electrostatic charge image developing toners 1 to 17 of Examples 1 to 17 all have a fixing temperature of 125 ° C. or less, and are excellent in low-temperature fixability. In addition, the electrostatic image developing toners 1 to 17 of Examples 1 to 17 all have a good storage stability evaluation and are excellent in storage stability. In addition, the electrostatic charge image developing toners 1 to 17 of Examples 1 to 17 all have a chargeability evaluation of “◯” and exhibit appropriate chargeability for use as a toner.

On the other hand, the electrostatic charge image developing toners 18 to 20, 26 and 30 of Comparative Examples 1 to 3, 9 and 13 have a poor storage stability evaluation and a poor storage stability. This is considered to be caused by the fact that in the electrostatic charge image developing toners 18 and 19 of Comparative Examples 1 and 2, the glass transition temperatures of the polyester resins Q1 and Q2 are 40 ° C. and lower than 50 ° C. In addition, in the electrostatic image developing toner 20 of Comparative Example 3, it is considered that the polyester resin Q3 has a weight average molecular weight of 5000 and is smaller than 7000. In the electrostatic image developing toner 26 of Comparative Example 9, (1) the glass transition temperature of the polyester resin Q9 is 40 ° C. and lower than 50 ° C., and (2) the weight average molecular weight of the polyester resin Q9 is 6000. Yes, it is considered to be caused by being smaller than 7000. In the electrostatic image developing toner 30 of Comparative Example 13, (1) the aromatic ring concentration of the polyester resin Q13 is 3.9 mol / kg and lower than 4.5 mol / kg, and (2) the polyester resin Q13 The glass transition temperature is 45 ° C, which is considered to be lower than 50 ° C.
Further, the electrostatic image developing toner 21 of Comparative Example 4 is inferior in low-temperature fixability because the fixing temperature is 150 ° C. and exceeds 130 ° C. This is considered to be due to the fact that in the electrostatic image developing toner 21 of Comparative Example 4, the weight average molecular weight of the polyester resin Q4 is 70000, which is larger than 50000. Further, the electrostatic image developing toner 22 of Comparative Example 5 has a fixing temperature of 145 ° C., which exceeds 130 ° C., and therefore has low temperature fixing properties. This is because, in the electrostatic charge image developing toner 22 of Comparative Example 5, the glass transition temperature of the polyester resin Q5 is 68 ° C., and the above formula 2: Tg = 2.67 × ln (Mw) + b (where 21. 07 ≦ b ≦ 39.48). Further, the electrostatic image developing toner 23 of Comparative Example 6 is inferior in low-temperature fixability because the fixing temperature is 140 ° C. and exceeds 130 ° C. This is because, in the electrostatic image developing toner 23 of Comparative Example 6, (1) the aromatic ring concentration of the polyester resin Q6 is 5.9 mol / kg, which is higher than 5.8 mol / kg, and (2) the polyester resin Q6. It is considered that the weight average molecular weight of is 60000 and is larger than 50000. Further, the electrostatic image developing toner 25 of Comparative Example 8 has a fixing temperature of 140 ° C., which exceeds 130 ° C., and thus has low temperature fixing properties. This is because, in the electrostatic image developing toner 25 of Comparative Example 8, (1) the aromatic ring concentration of the polyester resin Q8 is 5.9 mol / kg, which is higher than 5.8 mol / kg, and (2) the polyester resin Q8. The glass transition temperature is 69 ° C., and it is considered that the above-described formula 2: Tg = 2.67 × ln (Mw) + b (21.07 ≦ b ≦ 39.48) is not satisfied. Further, the electrostatic image developing toners 27, 28, and 29 of Comparative Examples 10, 11, and 12 have fixing temperatures of 140 ° C., 140 ° C., and 145 ° C., respectively, and are higher than 130 ° C. Inferior. This is because the aromatic ring concentrations of the polyester resins Q10, Q11, and Q12 in the electrostatic charge image developing toners 27, 28, and 29 of Comparative Examples 10, 11, and 12 are 5.9 mol / kg, 6.1 mol / kg, and 5 respectively. .9 mol / kg, which is considered to be caused by being larger than 5.8 mol / kg.
In addition, the electrostatic image developing toners 18 to 20, 24 and 16 of Comparative Examples 1 to 3, 7 and 9 have a chargeability evaluation of Δ and do not show appropriate chargeability for use as toners. This is considered to be because the electrostatic charge image developing toners 18 to 20 and 24 of Comparative Examples 1 to 3 and 7 have an acid value of 2 mgKOH / g and smaller than 3 mgKOH / g. Further, in the electrostatic charge image developing toner of Comparative Example 7, the glass transition temperature of the polyester resin Q7 is 64 ° C., and the above formula 1: Tg = 7.26 × ln (Mw) + a (where −19.33). ≦ a ≦ −4.29) is considered to be caused by not satisfying. In addition, in the electrostatic image developing toner 26 of Comparative Example 9, it is considered that the glass transition temperature of the polyester resin Q9 is 40 ° C. and is lower than 50 ° C.

  As mentioned above, although this invention was demonstrated in detail based on embodiment and an Example, this invention is not limited to this. It is obvious that those having ordinary knowledge in the relevant field can make modifications and improvements within the technical idea of the present invention.

Claims (11)

In the electrostatic image developing toner comprising at least a binder resin,
Including at least three elements selected from the group consisting of iron element, silicon element, sulfur element and fluorine element, including at least iron element, silicon element and sulfur element,
The content of the iron element is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm, the content of the silicon element is 1.0 × 10 ^{3 to} 5.0 × 10 ³ ppm, and the sulfur When the content of the element is 500 to 3000 ppm and the fluorine element is included, the content of the fluorine element is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ ppm,
The binder resin includes at least an amorphous polyester resin,
The amorphous polyester resin is
(1) The aromatic ring concentration is 4.5 to 5.8 mol / kg,
(2) The weight average molecular weight (Mw) is 7000-50000,
(3) The glass transition temperature (Tg) is 50 to 70 ° C.,
(4) An electrostatic charge image developing toner that satisfies Formula 1 when the weight average molecular weight (Mw) is 7000 or more and less than 14000, and satisfies Formula 2 when the weight average molecular weight (Mw) is 14000 or more and 50000 or less.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2   The amorphous polyester resin includes a structure derived from a polycarboxylic acid component in a repeating unit, and the polycarboxylic acid component has a substituent corresponding to three or more carboxyl groups. Toner for developing electrostatic images. The electrostatic charge image developing toner according to claim 1, wherein the amorphous polyester resin includes a repeating unit represented by any one of the general formulas (1) to (7).

(In the formula (1),
R1 represents a hydrogen atom, a carboxyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic aliphatic hydrocarbon group, or a substituted or unsubstituted An unsubstituted aromatic hydrocarbon group,
R2 is a carbonyl group, a sulfonyl group or an oxygen atom,
B represents a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic aliphatic hydrocarbon group, a substituted or unsubstituted aromatic carbon group. A functional group having a hydrogen group, a substituted or unsubstituted diphenylmethyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group at both ends and an ester bond inside, a substituted or unsubstituted linear aliphatic A functional group having a hydrocarbon group at both ends and having an ester bond and a urethane bond inside, a functional group having a substituted or unsubstituted branched aliphatic hydrocarbon group at both ends and an ester bond inside, substituted or A functional group having an unsubstituted branched aliphatic hydrocarbon group at both ends and an ester bond and a urethane bond inside, and a substituted or unsubstituted cyclic aliphatic hydrocarbon group at both ends A functional group having an ester bond inside, a substituted or unsubstituted cyclic aliphatic hydrocarbon group at both ends, and a functional group having an ester bond and a urethane bond inside, a substituted or unsubstituted aromatic hydrocarbon group A functional group having an ester bond inside, a substituted or unsubstituted aromatic hydrocarbon group at both ends, and a functional group having an ester bond and a urethane bond inside, substituted or unsubstituted diphenylmethyl A functional group having a group at both ends and an ester bond inside, or a functional group having a substituted or unsubstituted diphenylmethyl group at both ends and an ester bond and a urethane bond inside. )

(In formula (2), Cy is a saturated 4- to 6-membered ring, an unsaturated 4- to 6-membered ring, or a biphenyl group, and R1 and B have the same meanings as in formula (1).)

(In the formula (3), one of R3 is a hydrogen atom, a carboxyl group, a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic group. An aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group, the other of R3 is a carboxyl group, and B is as defined in Formula (1).)

(In Formula (4), R3 is synonymous with Formula (3), and B is synonymous with Formula (1).)

(In Formula (5), R3 and B are synonymous with Formula (1).)

(In Formula (6), R3 and B are synonymous with Formula (1).)

(In formula (7), D is a saturated or unsaturated hydrocarbon group in which at least one hydrogen atom is substituted with a carboxyl group, and B has the same meaning as in formula (1).)   The electrostatic image developing toner according to claim 3, wherein when B has a substituent, the substituent is a hydrocarbon group having 1 to 10 carbon atoms.   The electrostatic charge image developing toner according to claim 3, wherein the amorphous polyester-based resin contains 0.02 to 0.35 mol / kg of the repeating unit. The binder resin includes a crystalline polyester resin,
The crystalline polyester resin is
(A) The endothermic amount upon melting by differential scanning calorimetry is 2.0-10.0 W / g,
(B) The weight average molecular weight is 5000-15000,
(C) In the endothermic curve in differential scanning calorimetry, the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature is 3 to 5 ° C.,
(D) including one or more elements selected from sulfur element and fluorine element including at least sulfur element,
(E) The toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein the content of the weight average molecular weight of 1000 or less is 1 to less than 10%. A coating layer is provided on the outer surface,
The electrostatic image developing toner according to claim 1, wherein the coating layer includes at least the amorphous polyester resin.   The electrostatic charge image developing toner according to claim 7, wherein the coating layer has a thickness of 0.2 to 1.0 μm.   The electrostatic image developing toner according to claim 1, which has an acid value of 3 to 25 mg KOH / g. Having a volume average particle size of 3-9 μm,
The number of particles having a number average particle diameter of 3 μm or less is 3% by number or less,
10. The ratio of the abundance of the particles having a particle diameter of 3 μm or less to the abundance of the particles having a number average particle diameter of 1 μm or less is 2.0 to 4.0, according to claim 1. Toner for developing electrostatic images. In a method for producing an electrostatic charge image developing toner comprising at least a binder resin,
The first polycarboxylic acid component and the polyol component are subjected to dehydration condensation in the presence of a catalyst at a temperature of 150 ° C. or lower, (i) the resin obtained by the dehydration condensation is urethane-extended in the presence of the polyisocyanate component, and then Elongate with a second polycarboxylic acid component having a substituent corresponding to 3 or more carboxyl groups to synthesize an amorphous polyester resin, or (ii) 3 resins obtained by dehydration condensation An amorphous polyester resin is synthesized by extending with a second polycarboxylic acid component having a substituent corresponding to one or more carboxyl groups, and then extending with urethane in the presence of a polyisocyanate component. A polyester resin synthesis step;
An amorphous polyester resin latex forming step of forming a latex of the amorphous polyester resin;
A crystalline polyester resin synthesis step of synthesizing a crystalline polyester resin by dehydrating and condensing an aliphatic polycarboxylic acid component and an aliphatic polyol component at a temperature of 100 ° C. or lower in the presence of a catalyst;
A crystalline polyester resin latex forming step for forming a latex of the crystalline polyester resin;
A mixed liquid forming step of mixing at least the amorphous polyester resin latex and the crystalline polyester resin latex to form a mixed liquid;
A primary agglomerated particle forming step of adding a flocculant to the mixed solution, aggregating the amorphous polyester resin and the crystalline polyester resin to form primary agglomerated particles;
A coated aggregated particle forming step of forming a coated aggregated particle by providing a coating layer formed from the amorphous polyester-based resin on the surface of the primary aggregated particle;
Fusing and coalescing the coated agglomerated particles at a temperature higher than the glass transition temperature of the amorphous polyester resin,
The amorphous polyester resin is
(1) The aromatic ring concentration is 4.5 to 5.8 mol / kg,
(2) The weight average molecular weight (Mw) is 7000-50000,
(3) The glass transition temperature (Tg) is 50 to 70 ° C.,
(4) When the weight average molecular weight (Mw) is 7000 or more and less than 14,000, the formula 1 is satisfied, and when the weight average molecular weight (Mw) is 14,000 or more and 50000 or less, the formula 2 is satisfied,
The crystalline polyester resin is
(A) The endothermic amount upon melting by differential scanning calorimetry is 2.0-10.0 W / g,
(B) The weight average molecular weight is 5000-15000,
(C) In the endothermic curve in differential scanning calorimetry, the difference between the endothermic start temperature at the time of temperature rise and the endothermic peak temperature is 3 to 5 ° C.,
(D) including one or more elements selected from sulfur element and fluorine element including at least sulfur element,
(E) The content of the weight average molecular weight of 1000 or less is less than 1 to 10%,
The catalyst contains at least one element selected from elemental sulfur and elemental fluorine including at least elemental sulfur,
The method for producing a toner for developing an electrostatic charge image, wherein the flocculant contains an iron element and a silicon element.
Tg = 7.26 × ln (Mw) + a (-19.33 ≦ a ≦ -4.29) ・ ・ Formula 1
Tg = 2.67 × ln (Mw) + b (However, 21.07 ≦ b ≦ 39.48) ・ ・ Formula 2