JP2019066725A - Toner and method for manufacturing toner - Google Patents

Abstract

To provide a toner excellent in low-temperature fixability, charge maintaining property, and adhesion with paper.SOLUTION: A toner contains toner particles containing a resin component. The resin component contains an ester group-containing olefinic copolymer A, and an acid radical and an ester group-containing olefinic copolymer B; the acid values of the olefinic copolymer A and olefinic copolymer B are specific values; the olefinic copolymer A has specific structures Y1 and Y2; the content of the structure Y2 in the olefinic copolymer A is 3 to 35 mass%; the olefinic copolymer B has specific structures Z1, Z2, and Z3; the content of the structure Z3 in the olefinic copolymer B is 1 to 20 mass%; the content of the olefinic copolymer A in the resin component is 50 mass% or more.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in electrophotography and a method of manufacturing the toner.

  In recent years, in the image formation, as the demand for energy saving has increased, efforts have been made to lower the fixing temperature of toner.

As a method for improving the low-temperature fixability of toner, Patent Documents 1 to 3 disclose a technology in which a toner particle contains a crystalline polyester resin having a sharp melting property, whose viscosity significantly decreases when the melting point is exceeded. .
Further, as another method, Patent Documents 4 to 10 disclose a technique for lowering the fixing temperature by containing a resin having a low glass transition temperature in toner particles.
Specifically, a toner having toner particles containing an ester group-containing olefin copolymer such as an ethylene-vinyl acetate copolymer or an ethylene-methyl acrylate copolymer as a resin having a low glass transition temperature is patented. It is disclosed by the documents 4-10.

Japanese Patent Publication No. 56-13943 Japanese Examined Patent Publication No. 62-39428 JP-A-4-120554 JP, 2011-107261, A JP-A-11-202555 JP-A-8-184986 JP-A-4-21860 JP-A-3-150576 JP-A-59-18954 JP-A-58-95750 JP, 2016-224422, A

When a crystalline polyester resin is used as a resin component of toner particles, excellent low temperature fixability is exhibited due to the sharp melt property of the crystalline polyester resin.
However, the crystalline polyester resin tends to have a low volume resistivity, and there is a problem in the charge retention of the toner.
Therefore, the present inventors attempted to achieve both the low temperature fixing property and the charge retention property by using a resin having a high volume resistivity and a low glass transition temperature (below room temperature) as a resin component of toner particles.
However, as disclosed in Patent Documents 4 to 8, sufficient low-temperature fixability can be obtained when forming an image at high speed only by partially containing the ester group-containing olefin copolymer in the toner particles. It was difficult.
Further, as disclosed in Patent Documents 9 and 10 and 11, when an ester group-containing olefin copolymer is used as a resin component (main resin) of toner particles, adhesion between toner (toner image) and paper is achieved. There was a problem that the sex was low.
In particular, when an image is formed by an electrophotographic method employing a pressure heating fixing method in which the pressure applied to the toner at the time of fixing is low, the problem of the decrease in the adhesion between the toner and the paper becomes remarkable. Therefore, when the fixed material after pressure heating / fixing is rubbed with an eraser or the like, there arises a problem that the toner is peeled off from the paper.
The present invention provides a toner excellent in low-temperature fixability, charge retention and adhesion to paper, and a method for producing the toner.

As a result of intensive investigations by the present inventors, it is possible to use an ester group-containing olefin copolymer as a main resin for toner particles and further to use an acid group and an ester group-containing olefin copolymer in combination to achieve low temperature fixability. It was found that a toner excellent in charge retention and adhesion to paper was obtained.
The ethylene-based ester group-containing copolymer and the acid group- and ester group-containing olefin-based copolymer have higher compatibility than the similarity in chemical structure. Therefore, it is considered that the two coexist in the state where no significant phase separation occurs in the toner particles.
Furthermore, since the acid group- and ester group-containing olefin copolymer has an ester group, the crystallinity of the olefin is inhibited compared to the acid group-containing olefin copolymer having no ester group, and thus the melting point is lowered. It is thought that.
The acid group of the acid group- and ester group-containing olefin copolymer is considered to form a hydrogen bond with the hydroxyl group of the surface of the paper at the time of fixing. From the above reasons, the toner is considered to exhibit high low temperature fixability and high adhesion to paper.

That is, the present invention
A toner having toner particles containing a resin component,
The resin component contains an ester group-containing olefin copolymer A, and an acid group and an ester group-containing olefin copolymer B,
The acid value of the olefin copolymer A is 0 mg KOH / g or more and 10 mg KOH / g or less,
The acid value of the olefin copolymer B is 50 mg KOH / g or more and 250 mg KOH / g or less,
The olefin copolymer A is
A structure Y1 represented by the following formula (1),
And at least one structure Y2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3),
The content of the structure Y2 in the olefin copolymer A is 3% by mass or more and 35% by mass or less,
The olefin copolymer B is
A structure Z1 represented by the following formula (4),
A structure Z2 represented by the following formula (5),
And at least one structure Z3 selected from the group consisting of a structure represented by the following formula (6) and a structure represented by the following formula (7):
The content of the structure Z3 in the olefin copolymer B is 1% by mass or more and 20% by mass or less,
The content of the olefin copolymer A in the resin component is 50% by mass or more.

Also, the present invention is
A method for producing a toner having toner particles containing a resin component, comprising:
The resin component contains an ester group-containing olefin copolymer A, and an acid group and an ester group-containing olefin copolymer B,
Preparing a fine resin particle dispersion, wherein fine resin particles for producing the resin component are dispersed in an aqueous medium,
Aggregating the resin fine particles to form aggregate particles, and
Heating the aggregate particles to fuse them,
The acid value of the olefin copolymer A is 0 mg KOH / g or more and 10 mg KOH / g or less,
The acid value of the olefin copolymer B is 50 mg KOH / g or more and 250 mg KOH / g or less,
The olefin copolymer A is
A structure Y1 represented by the following formula (1),
And at least one structure Y2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3),
The content of the structure Y2 in the olefin copolymer A is 3% by mass or more and 35% by mass or less,
The olefin copolymer B is
A structure Z1 represented by the following formula (4),
A structure Z2 represented by the following formula (5),
And at least one structure Z3 selected from the group consisting of a structure represented by the following formula (6) and a structure represented by the following formula (7):
The content of the structure Z3 in the olefin copolymer B is 1% by mass or more and 20% by mass or less,
The content of the olefin copolymer A in the resin component is 50% by mass or more.

（該式（１）〜（７）中、Ｒ^１はＨ又はＣＨ_３を示し、Ｒ^２はＨ又はＣＨ_３を示し、Ｒ^３はＣＨ_３又はＣ_２Ｈ_５を示し、Ｒ^４はＨ又はＣＨ_３を示し、Ｒ^５はＣＨ_３又はＣ_２Ｈ_５を示し、Ｒ^６はＨ又はＣＨ_３を示し、Ｒ^７はＨ又はＣＨ_３を示し、Ｒ^８はＨ又はＣＨ_３を示
し、Ｒ^９はＣＨ_３、Ｃ_２Ｈ_５、Ｃ_３Ｈ_７又はＣ_４Ｈ_９を示し、Ｒ^１０はＨ又はＣＨ_３を示し、Ｒ^１１はＣＨ_３、Ｃ_２Ｈ_５、Ｃ_３Ｈ_７又はＣ_４Ｈ_９を示す。）

(In the formulas (1) to (7), R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , and R ⁴ represents H or indicates CH _3, ^{R 5} represents a CH ₃ or _C 2 _{H 5,} ^{R 6} represents H or CH _3, ^{R 7} represents H or CH _3, ^{R 8} represents H or CH _3, ^{R 9} Represents CH ₃ , C ₂ H ₅ , C ₃ H ₇ or C ₄ H ₉ , R ¹⁰ represents H or CH ₃ , R ¹¹ represents CH ₃ , C ₂ H ₅ , C ₃ H ₇ or C ₄ H ₉ ))

Also, the present invention is
A toner having toner particles containing a resin component,
The resin component is
An ethylene-vinyl acetate copolymer having an acid value of 0 mg KOH / g to 10 mg KOH / g,
And at least one of an ethylene-vinyl acetate-acrylic acid copolymer and an ethylene-vinyl acetate-methacrylic acid copolymer, having an acid value of 50 mgKOH / g or more and 250 mgKOH / g or less,
The content of the ethylene-vinyl acetate copolymer in the resin component is 50% by mass or more,
The content of vinyl acetate-derived monomer units in the ethylene-vinyl acetate copolymer is 3% by mass or more and 35% by mass or less,
The content of monomer units derived from vinyl acetate in at least one of the ethylene-vinyl acetate-acrylic acid copolymer and the ethylene-vinyl acetate-methacrylic acid copolymer is 1% by mass or more and 20% by mass or less Toner.

Also, the present invention is
A method for producing a toner having toner particles containing a resin component, comprising:
Preparing a fine resin particle dispersion, wherein fine resin particles for producing the resin component are dispersed in an aqueous medium,
Aggregating the resin fine particles to form aggregate particles, and
Heating the aggregate particles to fuse them,
The resin component is
An ethylene-vinyl acetate copolymer having an acid value of 0 mg KOH / g to 10 mg KOH / g,
At least one copolymer selected from the group consisting of an ethylene-vinyl acetate-acrylic acid copolymer and an ethylene-vinyl acetate-methacrylic acid copolymer, having an acid value of 50 mg KOH / g or more and 250 mg KOH / g or less Contains
The content of the ethylene-vinyl acetate copolymer in the resin component is 50% by mass or more,
The content of vinyl acetate-derived monomer units in the ethylene-vinyl acetate copolymer is 3% by mass or more and 35% by mass or less,
The content of monomer units derived from vinyl acetate in at least one copolymer selected from the group consisting of ethylene-vinyl acetate-acrylic acid copolymer and ethylene-vinyl acetate-methacrylic acid copolymer is 1 It is a method for producing a toner characterized in that the content is not less than 20% by mass.

  According to the present invention, it is possible to provide a toner excellent in low-temperature fixability, charge retention property and adhesion to paper, and a method for producing the toner.

In the present invention, the descriptions of “more than or equal to or less than xxx” and “o to xxx” indicating numerical ranges mean numerical ranges including the lower limit and the upper limit which are end points unless otherwise noted.
Moreover, a monomer unit means the reacted form of the monomer substance in a polymer or resin.
The crystalline resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).
Further, the resin component of the toner particles refers to a polymer component mainly contributing to the fixing performance.

The resin component contains an ester group-containing olefin copolymer A (hereinafter, also simply referred to as an olefin copolymer A).
The olefin copolymer A may be contained singly or in combination in the resin component.
The olefin copolymer A is a polymer in which a structure having an ester group is introduced to a polyolefin skeleton by means such as copolymerization.
Specifically, a structure Y1 represented by the following formula (1), and at least one structure Y2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3) Have.

In the formulas (1) to (3), R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , and R ⁴ represents H or CH. ₃ is shown, and R ⁵ is CH ₃ or C ₂ H ₅ .

Specific examples of the olefin copolymer A include ethylene-vinyl acetate copolymers in which R ¹ is H, R ² is H, and R ³ is CH ₃ in the above formula.
The ethylene-vinyl acetate copolymer is preferable from the viewpoint of low-temperature fixability because it can be designed to have a low melting point.
As another specific example, an ethylene-methyl acrylate copolymer in which R ¹ is H, R ⁴ is H, and R ⁵ is CH ₃ in the above formula; R ¹ is H, R ⁴ is H in the above formula Ethylene-ethyl acrylate copolymer in which R ⁵ is C ₂ H ₅ ; ethylene-methyl methacrylate copolymer in which R ¹ is H, R ⁴ is CH ₃ and R ⁵ is CH ₃ in the above formula A combination etc. are mentioned. These are preferable from the viewpoint of storage stability of the toner under high temperature and high humidity because they have high chemical stability.

In addition, the total mass of the olefin copolymer A is represented by W,
Let l be the mass of the structure shown in equation (1),
Let m be the mass of the structure shown in equation (2),
When the mass of the structure represented by the equation (3) is n,
From the viewpoint of low temperature fixability and charge retention, the value of (l + m + n) / W in the olefin copolymer A contained in the resin component is preferably 0.80 or more, and is 0.95 or more. Is more preferable, and 1.00 is more preferable.
The olefin copolymer A may contain a structure other than the structure Y1 and the structure Y2. There is no particular limitation as long as the effects of the present invention are not impaired, but examples include a structure represented by the following formula (8) and a structure represented by the following formula (9).
These can be introduced by adding a monomer corresponding to these structures in the copolymerization reaction for producing the olefin copolymer A, or modifying the olefin copolymer A by a polymer reaction it can.

（該式（８）及び（９）中、Ｒ^１２はＨ又はＣＨ_３を示し、Ｒ^１３はＨ又はＣＨ_３を示す。）

(In the formulas (8) and (9), R ¹² represents H or CH ₃ , and R ¹³ represents H or CH _3. )

From the viewpoint of charge retention of the toner, the acid value of the olefin copolymer A is 0 mg KOH / g or more and 10 mg KOH / g or less.
The acid value is preferably 5 mg KOH / g or less, more preferably substantially 0 mg KOH / g.

Further, from the viewpoint of low temperature fixability of the toner, the content of the olefin copolymer A in the resin component is 50% by mass or more with respect to the total mass of the resin component.
The content is preferably 70% by mass or more. The upper limit is not particularly limited, but is preferably 90% by mass or less.
The olefin copolymer A has a glass transition temperature of 0 ° C. or less, so when the content in the resin component is 50% by mass or more, the low-temperature fixability becomes good.
Further, the content of the structure Y2 in the olefin copolymer A is 3% by mass or more and 35% by mass or less from the viewpoint of charge retention and low-temperature fixability. The content is preferably 5% by mass or more and 20% by mass or less.
When the content of the structure Y2 in the olefin copolymer A is 35% by mass or less, the charge retention of the toner is improved. In addition, when the content is 20% by mass or less, the storage stability of the toner is further improved.
On the other hand, when the content of the structure Y2 in the olefin copolymer A is 3% by mass or more, the low temperature fixability is improved.
For example, in the case of ethylene-vinyl acetate copolymer, the content of the vinyl acetate-derived monomer unit in the ethylene-vinyl acetate copolymer is 3% by mass or more and 35% by mass or less.
In the ethylene-vinyl acetate copolymer, a monomer unit derived from vinyl acetate corresponds to Structure Y2.

The mass [l], [m], and [n] of the monomer unit represented by each of the above formulas, and the content of the structure Y2 can be measured using a general analysis method.
For example, nuclear magnetic resonance (NMR) or thermal decomposition gas chromatography may be used.
Hereinafter, the measuring method using < ¹ > H-NMR is shown.
For example, it is bonded to a hydrogen atom of alkylene in a structure represented by Formula (1), a hydrogen atom of an acetyl group or a propionyl group in a structure represented by Formula (2), or an oxygen in a structure represented by Formula (3) The content ratio of each structure can be calculated by comparing the integral value of the hydrogen atom of a methyl group or an ethyl group.
Specifically, the content ratio of each structure in the ethylene-vinyl acetate copolymer is calculated by the following method.
Device: JNM-ECZR series FT NMR (manufactured by JEOL Nippon Denshi Co., Ltd.)
In 0.5 mL of heavy acetone containing tetramethylsilane as an internal standard of 0.00 ppm,
A solution in which about 5 mg of a sample is dissolved is placed in a sample tube, and a ¹ H-NMR spectrum is measured under the conditions of a repetition time of 2.7 seconds and an integration number of 16 times.
The peaks at 1.14 to 1.36 ppm correspond to CH ₂ —CH ₂ in the structure derived from ethylene, and the peak near 2.04 ppm corresponds to CH ₃ in the structure derived from vinyl acetate. The ratio of the integral value of those peaks is calculated, and the content ratio of each structure is calculated.
The separation of the ester group-containing olefin copolymer A, acid group and ester group-containing olefin copolymer B, etc. from the toner is carried out using the difference in solubility in methyl ethyl ketone (MEK), toluene, tetrahydrofuran, etc. It is good to do.

The melt flow rate of the olefin copolymer A is preferably 5 g / 10 minutes to 30 g / 10 minutes, and more preferably 5 g / 10 minutes to 20 g / 10 minutes.
When the melt flow rate is 30 g / 10 min or less, the reduction in strength as a toner is suppressed, and the storage stability is improved.
On the other hand, when the melt flow rate is 5 g / 10 min or more, the gloss of the image is excellent.
The melt flow rate is measured under the conditions of a temperature of 190 ° C. and a load of 2160 g based on JIS K 7210.
When a plurality of olefin copolymers A are contained in the resin component, the measurement may be performed under the above conditions after melt mixing.
The melt flow rate can be controlled by changing the molecular weight of the olefin copolymer A. The melt flow rate can be reduced by increasing the molecular weight.

The weight average molecular weight (Mw) of the olefin copolymer A is preferably 50,000 or more, and more preferably 100,000 or more.
On the other hand, the weight average molecular weight is preferably 500000 or less from the viewpoint of image gloss.
The elongation at break of the olefin copolymer A is preferably 300% or more, and more preferably 500% or more. By setting the breaking elongation to 300% or more, the bending resistance of the fixed material is improved. The upper limit of the breaking elongation is about 1000% or less.
The breaking elongation was measured under the conditions based on JIS K 7162. In the case where a plurality of the ester group-containing olefin copolymers A are contained in the resin component, the measurement was carried out under the above conditions after melt mixing.

The resin component contains an acid group- and ester group-containing olefin copolymer B (hereinafter, also simply referred to as an olefin copolymer B).
The olefin copolymer B may be contained singly or in combination in the resin component.
By containing the olefin copolymer B, the acid group (for example, carboxy group) of the olefin copolymer B forms a hydrogen bond with the hydroxyl group on the surface of the paper. By this effect, the adhesion between the toner (toner image) and the paper is enhanced, and the fixed material is prevented from disappearing with the eraser.
Moreover, since the olefin copolymer B has an ester group, the crystallinity of the olefin is inhibited and the melting point is lowered. This effect improves the low temperature fixability.
The acid group- and ester group-containing olefin copolymer B has a monomer unit derived from a compound having an acid group and a monomer unit derived from a compound having an ester group in the polyolefin skeleton by means such as copolymerization. It is a macromolecule introduced into the molecule.
Specifically, it comprises a structure Z1 represented by the following formula (4), a structure Z2 represented by the following formula (5), a structure represented by the following formula (6), and a structure represented by the following formula (7) It has at least one structure Z3 selected from the group.

In the formulas (4) to (7), R ⁶ represents H or CH ₃ , R ⁷ represents H or CH ₃ , R ⁸ represents H or CH ₃ , and R ⁹ represents CH ₃ or C ₂ H. _{5 represents} C ₃ H ₇ or C ₄ H ₉ ; R ¹⁰ represents H or CH ₃ ; R ¹¹ represents CH ₃ , C ₂ H ₅ , C ₃ H ₇ or C ₄ H ₉ ;

Examples of the structure Z2 represented by the formula (5) include a structure derived from acrylic acid in which R ^{7 in} the formula is H, and a structure derived from methacrylic acid in which R ^{7 in} the formula is CH ₃ .
Adhesiveness with paper improves because the olefin copolymer B contains such a structure.
On the other hand, as the structure Z3, a structure derived from vinyl acetate in which R ⁸ in formula (6) is H and R ⁹ is CH ₃ , R ¹⁰ in formula (7) is H, R ¹¹ is A structure derived from methyl acrylate which is CH ₃ , a structure derived from ethyl acrylate in which R ¹⁰ in the formula (7) is H and R ¹¹ is C ₂ H ₅ , R ¹⁰ in the formula (7) is H And a structure derived from butyl acrylate in which R ¹¹ is C ₄ H ₉ , a structure derived from methyl methacrylate in which R ¹⁰ in formula (7) is CH ₃ , and R ¹¹ is CH ₃ , and the like. .
The olefin copolymer B is preferably designed from the viewpoint of low-temperature fixability because the melting point can be designed low by containing these structures.
Among them, R ⁶ in the formula (4) is H, R ⁷ in the formula (5) is H, R ⁸ in the formula (6) is H, and R ⁹ is CH ₃ , Ethylene-vinyl acetate-acrylic acid copolymer,
Or, R ⁶ in the formula (4) is H, R ⁷ in the formula (5) is CH ₃ , R ⁸ in the formula (6) is H, and R ⁹ is CH ₃ , Ethylene-vinyl acetate-methacrylic acid copolymer is preferable because higher-order low-temperature fixability, charge retention and adhesion to paper can be achieved at the same time.

The combination of the structure Z2 and the structure Z3 constituting the olefin copolymer B is not limited to the combination as long as it is the structure mentioned in the structure Z2 and the structure Z3.
Further, the olefin copolymer B may contain other structures other than the structure Z1, the structure Z2 and the structure Z3 to such an extent that the physical properties are not affected.
The content of the other structure in the olefin copolymer B is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and substantially 0% by mass. % Is particularly preferred.

The content of the olefin copolymer B in the resin component is preferably 10% by mass or more and less than 50% by mass, and more preferably 10% by mass or more and 30% by mass or less.
When the content of the olefin copolymer B is in the above range, adhesion to paper and charge retention are further improved.
The content of the structure Z3 in the olefin copolymer B is 1% by mass or more and 20% by mass or less. Moreover, it is preferable that this content is 5 mass% or more and 10 mass% or less.
When the content of the structure Z3 in the olefin copolymer B is 20% by mass or less, the charge retention of the toner is improved.
On the other hand, when the content of the structure Z3 in the olefin copolymer B is 1% by mass or more, the melting point is lowered and the low temperature fixing property is improved.

The acid value of the olefin copolymer B is 50 mg KOH / g or more and 250 mg KOH / g or less. The acid value is preferably 80 mg KOH / g or more and 200 mg KOH / g or less.
When the acid value is 50 mg KOH / g or more, adhesion between the toner and the paper is sufficiently developed. On the other hand, when the acid value is 250 mg KOH / g or less, the charge retention of the toner is improved.
The acid value of the olefin copolymer B can be controlled by the content of the structure Z2.

The melt flow rate of the olefin copolymer B is preferably 200 g / 10 min or less. When the melt flow rate is 200 g / 10 min or less, storage stability is improved.
Further, from the viewpoint of adhesion between toner and paper, the melt flow rate is preferably 10 g / 10 min or more. When the melt flow rate is 10 g / 10 min or more, it becomes easy to be compatible with the olefin copolymer A present in the toner, and the adhesion to the paper is improved in the whole toner.

  The melting point of the olefin copolymer B is preferably 50 ° C. or more and 100 ° C. or less from the viewpoint of low-temperature fixability and storage stability. When the melting point is 100 ° C. or less, the low temperature fixability is further improved. In addition, when the melting point is 90 ° C. or less, the low temperature fixability is further improved. On the other hand, when the melting point is 50 ° C. or more, storage stability is improved.

As the resin component, in addition to the olefin copolymer A and the olefin copolymer B, another polymer or resin may be used in combination as long as the effects of the present invention are not impaired.
Specifically, homopolymers of styrene and its substitution products such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene, etc .; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinyl naphthalene Copolymers, styrene copolymers such as styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer; polyvinyl chloride, phenolic resin, natural resin modified phenolic resin, natural resin modified maleic acid resin, acrylic Resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyethylene resin, polypropylene resin, etc. may be mentioned.

The toner particles may contain an aliphatic hydrocarbon compound.
The content of the aliphatic hydrocarbon compound is preferably 1 part by mass or more and 40 parts by mass or less, and 10 parts by mass or more, with respect to 100 parts by mass of the resin component, from the viewpoint of low temperature fixability and charge retention. More preferably, it is 35 parts by mass or less.
The melting point of the aliphatic hydrocarbon compound is preferably 50 ° C. or more and 100 ° C. or less, and more preferably 70 ° C. or more and 100 ° C. or less.
The aliphatic hydrocarbon compound can plasticize the olefin copolymer A upon heating. Therefore, by containing the aliphatic hydrocarbon compound in the toner particles, the olefin copolymer A forming the matrix at the time of heating and fixing of the toner can be plasticized to further improve the low temperature fixing property.
Furthermore, an aliphatic hydrocarbon compound having a melting point of 50 ° C. or more and 100 ° C. or less can also function as a nucleating agent of the olefin copolymer A. For this reason, micro mobility of the olefin copolymer A is suppressed, and charge retention is improved.
Specific examples of the aliphatic hydrocarbon compound include aliphatic hydrocarbons having 20 to 60 carbon atoms such as hexacosane, triacontane, and hexatriacontane.

The toner particles may contain silicone oil as a release agent.
The releasing agent generally used for toners such as alkyl wax is easily compatible with the olefin copolymer A, and the releasing effect is hardly obtained.
When the toner particles contain a colorant, the addition of the silicone oil improves the dispersibility of the colorant and makes it easy to obtain a high density image.
As silicone oil, dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, amino modified silicone oil, carboxy modified silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, etc. can be used.
The kinematic viscosity of the silicone oil is preferably 5 mm ² / s or more and 1000 mm ² / s or less, and more preferably 20 mm ² / s or more and 1000 mm ² / s or less.
The content of the silicone oil is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component from the viewpoint of obtaining good separability while suppressing the decrease in fluidity. It is more preferable that it is a mass part or more and 20 mass parts or less.

The toner particles may contain a colorant. Examples of the colorant include the following.
Examples of black colorants include those black-colored by using carbon black; yellow colorants, magenta colorants and cyan colorants.
Among these colorants, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full color image to improve the sharpness by using a dye and a pigment in combination.
As pigments for magenta toners, the following may be mentioned.
C. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following.
C. I. Solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disperse thread 9; C.I. I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
Examples of pigments for cyan toner include the following.
C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment having a phthalocyanine skeleton substituted with one or more and five or less phthalimidomethyl groups.
As dyes for cyan toner, C.I. I. Solvent Blue 70 is mentioned.
Examples of pigments for yellow toners include the following.
C. I. Pigment yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13,
14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 155, 155, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat Yellow 1, 3, 20.
As dyes for yellow toner, C.I. I. Solvent Yellow 162 can be mentioned.
These colorants can be used alone or in combination, or in the form of a solid solution.
The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner.
The content of the coloring agent is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component.

  The toner particles preferably have a volume-based median diameter of 3.0 μm or more and 10.0 μm or less, and more preferably 4.0 μm or more and 7.0 μm or less, from the viewpoint of obtaining a high-definition image. The volume-based median diameter of the toner particles may be measured using a particle size distribution analyzer (Coulter Multisizer III manufactured by Coulter) by the Coulter method.

The method for producing the toner of the present invention will be described.
The toner of the present invention can be produced by any method, but is preferably produced by the emulsion aggregation method described later. An acid group (for example, a carboxy group) contained in the olefin copolymer B tends to be present on the surface of the emulsified particle, and aggregation control becomes easy. As a result, the particle size distribution becomes sharp. In addition, since the acid group (for example, a carboxy group) contained in the olefin copolymer B is easily present on the surface of the toner particle, the effect of improving the adhesion to paper is large.
The emulsion aggregation method is a manufacturing method of preparing toner particles by preparing in advance a resin fine particle dispersion sufficiently small with respect to a target particle diameter, and aggregating the resin fine particles in an aqueous medium.

The method for producing the toner of the present invention is
A method for producing a toner having toner particles containing a resin component, comprising:
The resin component contains an ester group-containing olefin copolymer A, and an acid group and an ester group-containing olefin copolymer B,
Preparing a fine resin particle dispersion, wherein fine resin particles for producing the resin component are dispersed in an aqueous medium,
Aggregating the resin fine particles to form aggregate particles, and
Heating the aggregate particles to fuse them,
The acid value of the olefin copolymer A is 0 mg KOH / g or more and 10 mg KOH / g or less,
The acid value of the olefin copolymer B is 50 mg KOH / g or more and 250 mg KOH / g or less,
The olefin copolymer A is
A structure Y1 represented by the above formula (1),
And at least one structure Y2 selected from the group consisting of a structure represented by the above formula (2) and a structure represented by the above formula (3),
The content of the structure Y2 in the olefin copolymer A is 3% by mass or more and 35% by mass or less,
The olefin copolymer B is
A structure Z1 represented by the above formula (4),
A structure Z2 represented by the above formula (5),
And at least one structure Z3 selected from the group consisting of a structure represented by the above formula (6) and a structure represented by the above formula (7),
The content of the structure Z3 in the olefin copolymer B is 1% by mass or more and 20% by mass or less,
The content of the olefin copolymer A in the resin component is 50% by mass or more.

The production method comprises the steps (1) of preparing a resin fine particle dispersion, wherein resin fine particles for producing a resin component are dispersed in an aqueous medium, step (2) of aggregating the resin fine particles to form aggregate particles. And the step (3) of heating and fusing the aggregate particles.
In addition to the above-described steps, if necessary, a cooling step, a washing step, a drying step, and the like may be performed after the step (3).

Hereinafter, the method for producing a toner using the emulsion aggregation method will be specifically described, but it is not limited thereto.
<Step (1) of Preparing Resin Fine Particle Dispersion>
The fine resin particle dispersion can be prepared by a known method, but the following method can be suitably exemplified.
For example, the olefin copolymer A and the olefin copolymer B are dissolved in an organic solvent to form a uniform solution. Thereafter, a basic compound and a surfactant are added as needed. Further, an aqueous medium is added to the solution to form fine particles. Finally, the organic solvent is removed to prepare a resin fine particle dispersion in which the resin fine particles are dispersed.
In the step (1), the olefin copolymer A and the olefin copolymer B, and, if necessary, other components may be separately dispersed. Alternatively, two or more types of resin components may be converted to resin fine particles by a co-emulsification method.
When resin particles are formed by co-emulsification of the olefin copolymer A and the olefin copolymer B, the olefin copolymer A and the olefin copolymer B in the finely divided organic phase are Mix in particles. As a result, the compatibility between the two in the toner particles is enhanced, and the adhesion between the toner and the paper is further enhanced.
More specifically, the olefin copolymer A and the olefin copolymer B are heated and dissolved in an organic solvent, and a surfactant and a basic compound are added. Subsequently, a co-emulsion (resin fine particle dispersion) containing a resin component is prepared by slowly adding the aqueous medium in the presence of a surfactant while applying shear force with a homogenizer or the like.
Alternatively, after addition of the aqueous medium, a shear force is applied by a homogenizer or the like to prepare a co-emulsion containing the resin component.
Then, the co-emulsion liquid (resin particle dispersion liquid) of resin microparticles is produced by heating or pressure-removing and removing an organic solvent.

When preparing the fine resin particle dispersion, the addition amount of the resin component to be dissolved in the organic solvent is preferably 10 parts by mass to 50 parts by mass and 30 parts by mass to 50 parts by mass with respect to 100 parts by mass of the organic solvent. It is more preferable that it is less than 1 part.
Any organic solvent can be used as long as it can dissolve the resin component, but a solvent having high solubility in an olefin copolymer A such as toluene, xylene, ethyl acetate or the like is preferable.
The surfactant is not particularly limited. For example, anionic surfactants of sulfate ester type, sulfonate type, carboxylate type, phosphate type, soap type; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol type, Examples thereof include alkylphenol ethylene oxide adduct type surfactants and polyhydric alcohol type nonionic surfactants.
Examples of the basic compound include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine, trimethylamine, dimethylaminoethanol and diethylaminoethanol. The basic compounds may be used alone or in combination of two or more.

The volume-based median diameter of the resin fine particles is preferably 0.05 μm or more and 1.00 μm or less, and more preferably 0.10 μm or more and 0.60 μm or less. When the median diameter is in the above range, toner particles having a desired particle diameter can be easily obtained.
The volume-based median diameter may be measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX 150: manufactured by Nikkiso Co., Ltd.).

<Step of Forming Aggregate Particles (2)>
In step (2), for example, the colorant fine particle dispersion, the aliphatic hydrocarbon fine particle dispersion, and the silicone oil emulsion are mixed with the above-mentioned resin fine particle dispersion, if necessary, to prepare a mixed solution, The step of aggregating fine particles contained in the prepared mixture liquid to form aggregate particles.
As a method of forming the aggregate particles, a method of adding and mixing an aggregating agent into the above mixed solution, raising the temperature, and appropriately adding mechanical power and the like can be suitably exemplified.
The colorant fine particle dispersion is prepared by dispersing the above-mentioned colorant. The colorant fine particles are dispersed by a known method, but for example, a media type disperser such as a rotary shear type homogenizer, a ball mill, a sand mill, an attritor, a high pressure counter collision type disperser, etc. are preferably used. In addition, surfactants and polymer dispersants that impart dispersion stability can be added as necessary.
The aliphatic hydrocarbon fine particle dispersion and the silicone oil emulsion are prepared by dispersing each material in an aqueous medium. Each material is dispersed by a known method, but for example, a media type dispersing machine such as a rotary shear type homogenizer, a ball mill, a sand mill, an attritor, a high pressure counter collision type dispersing machine, etc. are preferably used. In addition, surfactants and polymer dispersants that impart dispersion stability can be added as necessary.
Examples of the coagulant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; metal salts of trivalent metals such as iron and aluminum; polyaluminum chloride And polyvalent metal salts such as From the viewpoint of the particle diameter controllability of step (2), metal salts of divalent metals such as calcium chloride and magnesium sulfate are preferable.
The addition and mixing of the flocculant is preferably performed in a temperature range from room temperature to 75 ° C. When the above mixing is performed under this temperature condition, aggregation proceeds in a stable state. The above mixing can be carried out using a known mixing device, homogenizer, mixer or the like.
The volume-based median diameter of the aggregate particles formed in the step (2) is not particularly limited, but usually 4.0 μm or more and 7.0 μm or so to be the same as the median diameter of toner particles to be obtained. It is good to control below. The control can be easily performed, for example, by appropriately setting and changing the temperature at the time of addition and mixing of the coagulant and the like and the conditions of the stirring and mixing.
The volume-based median diameter of the aggregate particles may be measured using a particle size distribution analyzer (Coulter Multisizer III manufactured by Coulter) by the Coulter method.

<Step of fusing (3)>
The step (3) of coalescing is a step of manufacturing particles in which the surface of the aggregate particles is smoothed by heating and coalescing the aggregate particles, preferably above the melting point of the olefin copolymer A.
Before entering the step (3), a chelating agent, a pH adjusting agent, a surfactant and the like can be appropriately added in order to suppress fusion between the obtained resin particles.
Examples of chelating agents are alkali metal salts such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, sodium gluconate, sodium tartrate, potassium citrate and sodium citrate, nitrotriacetate (NTA) salts, both COOH and OH Water-soluble polymers (polyelectrolytes) that contain the functionality of
The heating temperature may be from the melting point or more of the olefin copolymer A contained in the aggregate particles to a temperature at which the olefin copolymer A or the olefin copolymer B is thermally decomposed. The heating and fusion time is short if the heating temperature is high and long if the heating temperature is low. That is, the time of heat fusion depends on the temperature of heating and can not be generally defined, but is generally about 10 minutes to 10 hours.

<Cooling process>
In the cooling step, it is preferable to cool the temperature of the aqueous medium containing the resin particles obtained in the step (3) to a temperature lower than the crystallization temperature of the olefin copolymer A.
By performing cooling to a temperature lower than the crystallization temperature, generation of coarse particles can be suppressed. A specific cooling rate is about 0.1 ° C./min to about 50 ° C./min.
Moreover, it is preferable to hold | maintain at temperature with a rapid crystallization rate of the olefin type copolymer A during cooling, or after cooling, and to perform the annealing which promotes crystallization. By maintaining the temperature at about 30 ° C. to 70 ° C., crystallization is promoted, and the blocking resistance of the toner is improved.

<Washing process>
Impurities in the resin particles can be removed by repeating washing and filtration of the resin particles produced through the above steps.
Specifically, it is preferable to wash the resin particles using an aqueous solution containing a chelating agent such as ethylenediaminetetraacetic acid (EDTA) and its Na salt and further washing with pure water.
Washing with pure water can remove metal salts in the resin particles, surfactants and the like by repeating filtration a plurality of times. The number of times of filtration is preferably 3 or more and 20 or less from the viewpoint of production efficiency, and more preferably 3 or more and 10 or less.

<Drying process>
The washed resin particles can be dried to obtain toner particles.
The toner particles may be used as toner as they are. In addition, if necessary, a toner fine particle such as silica fine particle, alumina fine particle, titania fine particle, calcium carbonate fine particle or the like, or resin fine particle such as vinyl resin, polyester resin, silicone resin etc. It may be added to particles to obtain a toner. These inorganic fine particles and resin fine particles function as external additives such as a flowability aid and a cleaning aid.

Hereinafter, methods of measuring various physical properties of the toner and the raw material will be described.
<Method of measuring acid number>
The acid value is the number of mg of potassium hydroxide required to neutralize an acid component such as free fatty acid and resin acid contained in 1 g of a sample. The measuring method is measured as follows according to JIS-K0070.
(1) Reagents and solvents: A mixture of toluene and ethyl alcohol (2: 1) is neutralized with a 0.1 mol / L potassium hydroxide ethyl alcohol solution with phenolphthalein as an indicator immediately before use.
Phenolphthalein solution: Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol (95% by volume).
0.1 mol / L potassium hydroxide ethyl alcohol solution: 7.0 g of potassium hydroxide is dissolved in as little water as possible, ethyl alcohol (95% by volume) is added to make it into 1 L, and it is left to stand for 2 to 3 days, and filtered. Standardization is performed according to JIS K 8006 (Basic matter about titration during content test of reagent).
(2) Operation 1 to 20 g of resin is precisely weighed as a sample, 100 mL of the solvent and a few drops of the phenolphthalein solution as an indicator are added thereto, and shaken sufficiently until the sample is completely dissolved. In the case of a solid sample, heat and dissolve on a water bath. After cooling, this is titrated with the above-mentioned 0.1 mol / L potassium hydroxide ethyl alcohol solution, and the end point of neutralization is taken as the slight red color of the indicator lasts for 30 seconds.
(3) Calculation formula The acid value is calculated by the following formula.
A = B × f × 5.611 / S
A: Acid value (mg KOH / g)
B: Use amount (mL) of 0.1 mol / L potassium hydroxide ethyl alcohol solution
f: Factor S of 0.1 mol / L potassium hydroxide ethyl alcohol solution S: mass of sample (g)

<Measuring method of melting point>
The melting point is measured using a differential scanning calorimeter (DSC).
Specifically, a sample of 0.01 to 0.02 g is precisely weighed in an aluminum pan and heated from 0 ° C. to 200 ° C. at a temperature rising rate of 10 ° C./min to obtain a DSC curve.
From the obtained DSC curve, the peak temperature of the endothermic peak is taken as the melting point.

  Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the number of parts and% of an Example and a comparative example are all mass references | standards unless there is particular notice.

<Production of resin fine particle 1 dispersion>
Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts Ethylene-vinyl acetate copolymer EVA-A 100 parts (in the formulas (1) and (2), R ¹ H H, R ² H H, R ³ CH CH ₃ , Content of structure Y2 in EVA-A: 15% by mass, acid value: 0 mg KOH / g, weight average molecular weight: 110000, melt flow rate: 12 g / 10 min, melting point: 86 ° C., elongation at break: 700%, l + m + n) /W=1.00)
· Ethylene-vinyl acetate-methacrylic acid copolymer B1 25 parts (in the formulas (4), (5) and (6), R ⁶ H H, R ⁷ CH CH ₃ , R ⁸ H H, R ⁹ CH CH ₃ , Content of structure Z3 in the ethylene-vinyl acetate-methacrylic acid copolymer B1: 6% by mass, melt flow rate: 60 g / 10 min, melting point: 82 ° C., acid value: 98 mg KOH / g, hereinafter simply It is also labeled "B1."
The above formulations were mixed and dissolved at 90 ° C.
Separately, 0.7 part of sodium dodecylbenzene sulfonate, 1.5 parts of sodium laurate and 3.6 parts of N, N-dimethylaminoethanol were added to 700 parts of ion-exchanged water, and the mixture was heated and dissolved at 90 ° C.
Then, the above-mentioned toluene solution and aqueous solution are mixed, and an ultra high speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primix Co., Ltd.).
Further, the mixture was emulsified at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Co., Ltd.).
Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (resin fine particle 1 dispersion) with a concentration of 20% of resin fine particles 1.
The volume-based median diameter of the resin fine particles 1 was measured using a dynamic light scattering type particle size distribution analyzer (Nanotrac: manufactured by Nikkiso Co., Ltd.) and was 0.40 μm.

<Production of resin fine particle 2 dispersion>
Production of resin fine particle 1 dispersion except that the amount of ethylene-vinyl acetate-methacrylic acid copolymer B1 used was changed to 11 parts and the amount of N, N-dimethylaminoethanol used was changed to 1.6 parts Similarly, a dispersion of fine resin particles 2 was obtained. The volume-based median diameter of the obtained resin fine particles 2 was 0.48 μm.

<Production of resin fine particle 3 dispersion>
Production of resin fine particle 1 dispersion except that the amount of ethylene-vinyl acetate-methacrylic acid copolymer B1 used was changed to 43 parts and the amount of N, N-dimethylaminoethanol used was changed to 6.1 parts Similarly, a dispersion of resin fine particles 3 was obtained. The volume-based median diameter of the obtained resin fine particles 3 was 0.33 μm.

<Production of Resin Fine Particle 4 Dispersion>
EVA-A is an ethylene-vinyl acetate copolymer EVA-B (in formulas (1) and (2), R ¹ H H, R ² H H, R ³ CHCH ₃ , structure Y 2 in EVA-B Content: 20% by mass, acid value: 0 mg KOH / g, melt flow rate: 14 g / 10 min, melting point: 75 ° C., elongation at break: 800%, (l + m + n) /W=1.00) A resin fine particle 4 dispersion was obtained in the same manner as in the production of resin fine particle 1 dispersion. The volume-based median diameter of the obtained resin fine particles 4 was 0.45 μm.

<Production of Resin Fine Particle 5 Dispersion>
EVA-A is an ethylene-vinyl acetate copolymer EVA-C (in formulas (1) and (2), R ¹ H H, R ² H H, R ³ CHCH ₃ , structure Y 2 in EVA-C Content: 28% by mass, acid value: 0 mg KOH / g, melt flow rate: 20 g / 10 min, melting point: 69 ° C., elongation at break: 800%, (l + m + n) /W=1.00) The resin fine particle 5 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion. The volume-based median diameter of the obtained resin fine particles 5 was 0.50 μm.

<Production of resin fine particle 6 dispersion>
EVA-A is an ethylene-vinyl acetate copolymer EVA-D (in formulas (1) and (2), R ¹ H H, R ² H H, R ³ CHCH ₃ , structure Y 2 in EVA-D Content: 6 mass%, acid value: 0 mg KOH / g, melt flow rate: 75 g / 10 min, melting point: 96 ° C., elongation at break: 460%, (l + m + n) /W=1.00) A resin fine particle 6 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion. The volume-based median diameter of the obtained resin fine particles 6 was 0.45 μm.

<Production of dispersion of resin fine particles 7>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-vinyl acetate-methacrylic acid copolymer B2 (in formulas (4), (5) and (6), R ⁶ HH, R ⁷ CHCH ₃ , R ⁸ H H, R ⁹ CH CH ₃ , Content of structure Z3 in ethylene-vinyl acetate-methacrylic acid copolymer B2: 8% by mass, melt flow rate: 35 g / 10 min, melting point: 86 ° C., acid value Resin fine particle 7 dispersion was obtained in the same manner as in the production of resin fine particle 1 dispersion, except that it was changed to 65 mg KOH / g, hereinafter simply referred to as "B2". The volume-based median diameter of the obtained resin fine particles 7 was 0.40 μm.

<Production of Dispersion of Resin Fine Particles 8>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-vinyl acetate-acrylic acid copolymer B3 (in formulas (4), (5) and (6), R ⁶ 6H, R ⁷ HH, R ^{8 = H, R 9 = CH} 3, ethylene - vinyl acetate - the content of the structural Z3 acrylic acid copolymer B3: 6 wt%, melt flow rate: 35 g / 10 min, melting point: 78 ° C., acid number: In the same manner as in the production of resin fine particle 1 dispersion, except that 163 mg KOH / g, hereinafter simply referred to as "B3", and the amount of N, N-dimethylaminoethanol used was changed to 6.5 parts. A dispersion of resin fine particles 8 was obtained. The volume-based median diameter of the obtained resin fine particles 8 was 0.32 μm.

<Production of resin fine particle 9 dispersion>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-vinyl acetate-methacrylic acid copolymer B4 (in formulas (4), (5) and (6), R ⁶ HH, R ⁷ CHCH ₃ , R ⁸ HH, R ⁹ CHCH ₃ , Content of structure Z3 in ethylene-vinyl acetate-methacrylic acid copolymer B4: 3% by mass, melt flow rate: 25 g / 10 min, melting point: 88 ° C., acid value Resin fine particle 9 dispersion was obtained in the same manner as in the production of resin fine particle 1 dispersion, except that it was changed to 90 mg KOH / g, hereinafter also simply referred to as "B4". The volume-based median diameter of the obtained resin fine particles 9 was 0.44 μm.

<Production of dispersion of resin fine particles 10>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-vinyl acetate-methacrylic acid copolymer B5 (in formulas (4), (5) and (6), R ⁶ HH, R ⁷ CHCH ₃ , R ⁸ H H, R ⁹ CH CH ₃ , Content of structure Z3 in ethylene-vinyl acetate-methacrylic acid copolymer B5: 15% by mass, melt flow rate: 25 g / 10 min, melting point: 73 ° C., acid value Resin fine particle 10 dispersion was obtained in the same manner as in the production of resin fine particle 1 dispersion, except that it was changed to 90 mg KOH / g, hereinafter simply referred to as "B5". The volume-based median diameter of the obtained resin fine particles 10 was 0.36 μm.

<Production of Dispersion of Fine Resin Particles 11>
EVA-A is ethylene-ethyl acrylate copolymer EEA-A (in formulas (1) and (3), R ¹ H H, R ⁴ H H, R ⁵ CC ₂ H ₅ , in EEA-A Content of structure Y2: 25% by mass, acid value: 0 mg KOH / g, melt flow rate: 20 g / 10 min, melting point: 91 ° C., elongation at break: 900%, (l + m + n) /W=1.00) A resin fine particle 11 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion except for the above. The volume-based median diameter of the obtained resin fine particles 11 was 0.40 μm.

<Production of dispersion of resin fine particles 12>
100 parts of EEA-A were dissolved in 400 parts of dioxane at 100 ° C. Thereafter, 10 parts of pure water and 10 parts of sodium hydroxide were added, and refluxing was performed for 6 hours. After that, EEA-B was obtained by washing with ethanol. The acid value of EEA-B at this time was 9 mg KOH / g.
A resin fine particle 12 dispersion was obtained in the same manner as in the resin fine particle 1 dispersion except that EVA-A was changed to EEA-B and the amount of N, N-dimethylaminoethanol used was changed to 5.0 parts. The The volume-based median diameter of the obtained resin fine particles 12 was 0.28 μm.

<Production of dispersion of resin fine particles 13>
The EVA-A, ethylene - in methyl acrylate copolymer EMA-A (formula (1) and ^{(3), R 1 = H} , R 4 = H, R 5 = CH 3, the structure in EMA-A Y2 Content: 14 mass%, acid value: 0 mg KOH / g, melt flow rate: 14 g / 10 min, melting point: 87 ° C., elongation at break: 800%, (l + m + n) /W=1.00) In the same manner as in the production of the resin fine particle 1 dispersion, a resin fine particle 13 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles 13 was 0.42 μm.

<Production of dispersion of resin fine particles 14>
EVA-A is an ethylene-methyl methacrylate copolymer EMMA-A (in formulas (1) and (3), R ¹ H H, R ⁴ CHCH ₃ , R ⁵中 CH ₃ , structure in EMMA-A Content of Y2: 18 mass%, acid value: 0 mg KOH / g, melt flow rate: 7 g / 10 min, melting point: 89 ° C., elongation at break: 750%, (l + m + n) /W=1.00) A resin fine particle 14 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion except for the above. The volume-based median diameter of the obtained resin fine particles 14 was 0.44 μm.

<Production of dispersion of resin fine particles 15>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-ethyl acrylate-methacrylic acid copolymer B6 (in formulas (4), (5) and (7), R ⁶ HH, R ⁷ CHCH ₃ R ¹⁰ HH, R ¹¹ CC ₂ H ₅ , ethylene-ethyl acrylate-methacrylic acid copolymer B6 content of structure Z3: 6% by mass, melt flow rate: 14 g / 10 min, melting point: 89 A resin fine particle 15 dispersion was obtained in the same manner as in the resin fine particle 1 dispersion, except that the acid value was changed to 95 ° C KOH / g (hereinafter simply referred to as "B6"). The volume-based median diameter of the obtained resin fine particles 15 was 0.39 μm.

<Manufacture of resin fine particle 16 dispersion>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-methyl acrylate-methacrylic acid copolymer B7 (in formulas (4), (5) and (7), R ⁶ HH, R ⁷ CHCH ₃ R ¹⁰ HH, R ¹¹ CHCH ₃ , content of structure Z3 in ethylene-methyl acrylate-methacrylic acid copolymer B7: 6% by mass, melt flow rate: 23 g / 10 min, melting point: 87 ° C. An acid value: 72 mg KOH / g (hereinafter also simply referred to as "B7"), except that a dispersion of fine resin particles 1 was obtained, except that the dispersion of fine resin particles 1 was obtained. The volume-based median diameter of the obtained resin fine particles 16 was 0.41 μm.

<Production of dispersion of resin fine particles 17>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-methyl methacrylate-methacrylic acid copolymer B8 (in formulas (4), (5) and (7), R ⁶ HH, R ⁷ CHCH ₃ R ¹⁰ CHCH ₃ , R ¹¹ CHCH ₃ , ethylene-methyl methacrylate-methacrylic acid copolymer B8 content of structure Z3: 6% by mass, melt flow rate: 12 g / 10 min, melting point: 88 ° C. An acid value: 66 mg KOH / g (hereinafter also simply referred to as "B8"), except that a dispersion of resin fine particles 1 was obtained, in the same manner as in the production of resin fine particle 1 dispersion. The volume-based median diameter of the obtained resin fine particles 17 was 0.44 μm.

<Production of dispersion of resin fine particles 18>
EVA-A is ethylene-vinyl acetate-vinyl valerate copolymer EVA-E (in formulas (1) and (2), R ¹ = H, R ² HH, R ³ CHCH ₃ , EVA-E Content of structure Y2 of: 14% by mass, content of monomer units derived from vinyl valerate: 6% by mass, acid value: 0 mg KOH / g, melt flow rate: 14 g / 10 min, melting point: 83 ° C., elongation at break A resin fine particle 18 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion, except that the degree was changed to 750% and (l + m + n) /W=0.94. The volume-based median diameter of the obtained resin fine particles 18 was 0.42 μm.

<Production of dispersion of resin fine particles 19>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-vinyl acetate-methacrylic acid copolymer B9 (in formulas (4), (5) and (6), R ⁶ HH, R ⁷ CHCH ₃ , ^{R 8 = H, R 9 =} CH 3, ethylene - vinyl acetate - the content of the structural Z3 methacrylic acid copolymer B9: 6 wt%, melt flow rate: 14 g / 10 min, acid value: 24 mg KOH / g, Hereinafter, a dispersion of resin fine particles 19 was obtained in the same manner as in the production of the dispersion of resin fine particles 1 except that the solution was simply changed to “B9”. The volume-based median diameter of the obtained resin fine particles 19 was 0.51 μm.

<Production of dispersion of resin fine particles 20>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-vinyl acetate-acrylic acid copolymer B10 (in formulas (4), (5) and (6), R ⁶ HH, R ⁷ HH, R ⁸ = H, R ⁹ = CH ₃ , Content of structure Z3 in ethylene-vinyl acetate-acrylic acid copolymer B10:
6 mass%, melt flow rate: 160 g / 10 min, melting point: 70 ° C., acid value: 303 mg KOH / g, hereinafter, also simply referred to as "B10". A resin fine particle 20 dispersion was obtained in the same manner as in the resin fine particle 1 dispersion, except that the amount of N, N-dimethylaminoethanol was changed to 12.0 parts. The volume-based median diameter of the obtained resin fine particles 20 was 0.29 μm.

<Production of Dispersion of Fine Resin Particles 21>
EVA-A is an ethylene-vinyl acetate copolymer EVA-F (in formulas (1) and (2), R ¹ H H, R ² H H, R ³ CHCH ₃ , structure Y 2 in EVA-F Content: 2% by mass, acid value: 0 mg KOH / g, melt flow rate: 3 g / 10 min, melting point: 105 ° C., elongation at break: 600%, (l + m + n) /W=1.00) The resin fine particle 21 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion. The volume-based median diameter of the obtained resin fine particles 21 was 0.53 μm.

<Manufacture of fine resin particle 22 dispersion>
EVA-A is an ethylene-vinyl acetate copolymer EVA-G (in formulas (1) and (2), R ¹ H H, R ² H H, R ³ CHCH ₃ , structure Y 2 in EVA-G Content: 41% by mass, acid value: 0 mg KOH / g, melt flow rate: 2 g / 10 min, melting point: 40 ° C., elongation at break: 870%, (l + m + n) /W=1.00) The resin fine particle 22 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion. The volume-based median diameter of the obtained resin fine particles 22 was 0.53 μm.

<Production of dispersion of resin fine particles 23>
EVA-A is an ethylene-vinyl acetate copolymer EVA-H (in formulas (1) and (2), R ¹ H H, R ² H H, R ³ CHCH ₃ , structure Y 2 in EVA-H Content: 20% by mass, acid value: 0 mg KOH / g, melt flow rate: 200 g / 10 min, melting point: 75 ° C., elongation at break: 210%, (l + m + n) /W=1.00), ethylene -A fine resin particle 23 dispersion was obtained in the same manner as in the production of the fine resin particle 1 dispersion except that vinyl acetate-methacrylic acid copolymer B1 was not used. The volume-based median diameter of the obtained resin fine particles 23 was 0.22 μm.

<Production of dispersion of resin fine particles 24>
A resin fine particle 24 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion except that the ethylene-vinyl acetate-methacrylic acid copolymer B1 was not used. The volume-based median diameter of the obtained resin fine particles 24 was 5.51 μm.

<Production of dispersion of resin fine particles 25>
EVA-A is changed to ethylene-ethyl acrylate copolymer EEA-A, and it is carried out similarly to manufacture of resin fine particle 1 dispersion except having not used ethylene-vinyl acetate-methacrylic acid copolymer B1. Resin fine particle 25 dispersion liquid was obtained. The volume-based median diameter of the obtained resin fine particles 25 was 6.21 μm.

<Production of Dispersion of Fine Resin Particles 26>
Ethylene-vinyl acetate-methacrylic acid copolymer B1, ethylene-methacrylic acid copolymer B11 (in formulas (4) and (5), R ⁶ HH, R ⁷ CHCH ₃ , ethylene-methacrylic acid copolymer Content of structure Z3 in B11: Melt flow rate: 35 g / 10 min, melting point: 95 ° C., acid value: 60 mg KOH / g) A dispersion of resin fine particles 26 was obtained. The volume-based median diameter of the obtained resin fine particles 26 was 0.40 μm.

<Production of dispersion of resin fine particles 27>
Ethylene-vinyl acetate-methacrylic acid copolymer B1 is prepared by using ethylene-vinyl acetate-methacrylic acid copolymer B12 (in formulas (4), (5) and (6), R ⁶ = H, R ⁷ CHCH ₃ , ^{R 8 = H, R 9 =} CH 3, ethylene - vinyl acetate - the content of the structural Z3 methacrylic acid copolymer B12: 25 wt%, melt flow rate: 10 g / 10 min, melting point: 78 ° C., an acid value A dispersion of resin fine particles 27 was obtained in the same manner as in the production of the dispersion of resin fine particles 1 except that the dispersion was changed to 66 mg KOH / g). The volume-based median diameter of the obtained resin fine particles 27 was 0.30 μm.

<Production of dispersion of resin fine particles 28>
The amount of EVA-A was changed to 56.25 parts, the amount of ethylene-vinyl acetate-methacrylic acid copolymer B1 was changed to 68.75 parts, and the amount of N, N-dimethylaminoethanol used was 9 A resin fine particle 28 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion except that the amount was changed to 8 parts. The volume-based median diameter of the obtained resin fine particles 28 was 0.21 μm.

<Production of Dispersion of Fine Resin Particles 29>
EVA-A, polyester resin A [composition (molar ratio) [polyoxypropylene (2.2) -2, 2-bis (4-hydroxyphenyl) propane: isophthalic acid: terephthalic acid = 100: 50: 50], Number average molecular weight (Mn) = 4,600, weight average molecular weight (Mw) = 16,500, peak molecular weight (Mp) = 10,400, glass transition temperature (Tg) = 70 ° C., acid value: 13 mg KOH / g] A resin fine particle 29 dispersion was obtained in the same manner as in the production of the resin fine particle 1 dispersion except for the change. The volume-based median diameter of the obtained resin fine particles 29 was 0.22 μm.

<Production of dispersion of resin fine particles 30>
EVA-A and ethylene-vinyl acetate-methacrylic acid copolymer B1 are not used, and crystalline polyester resin A [composition (molar ratio) [1, 9-nonanediol: sebacic acid = 100: 100], number average molecular weight Except that the amount of (Mn) = 5,500, weight average molecular weight (Mw) = 15,500, peak molecular weight (Mp) = 11,400, melting point: 72 ° C., acid value: 13 mg KOH / g) was 125 parts Were obtained in the same manner as in the production of the resin fine particle 1 dispersion, to obtain a resin fine particle 30 dispersion. The volume-based median diameter of the obtained resin fine particles 30 was 0.25 μm.

<Manufacture of colorant fine particle dispersion>
-Coloring agent 10.0 parts (Cyan pigment made by Dainichiseika: Pigment Blue 15: 3)
・ Anionic surfactant (Dai-ichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.5 parts ・ ion-exchanged water 88.5 parts Mix the above and use high pressure impact type dispersing machine Nanomizer (Yoshida Kako Kogyo) The mixture was time-dispersed to prepare an aqueous dispersion (colorant particle dispersion liquid) having a concentration of 10% of colorant particles formed by dispersing the colorant. The volume-based median diameter of the obtained colorant fine particles was measured using a dynamic light scattering particle size distribution diameter (Nanotrac: manufactured by Nikkiso Co., Ltd.), and was 0.20 μm.

<Production of aliphatic hydrocarbon fine particle dispersion>
Aliphatic hydrocarbon compound (HNP-51, melting point 78 ° C., manufactured by Nippon Seiwa Co., Ltd.) 20.0 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 part After 0 parts or more were charged into a mixing vessel equipped with a stirrer, the mixture was heated to 90 ° C. and circulated to Clearmix W Motion (manufactured by M. Technique) to carry out dispersion treatment for 60 minutes. The conditions of the distributed processing were as follows.
・ Rotor outer diameter 3 cm
・ Clearance 0.3 mm
· Rotor speed 19000 rpm
・ Screen rotation speed 19000rpm
After dispersion treatment, cooling to 40 ° C. under cooling processing conditions with a rotor rotational speed of 1000 rpm, a screen rotational speed of 0 rpm, and a cooling speed of 10 ° C./min, an aqueous dispersion with a concentration of 20% of aliphatic hydrocarbon fine particles (aliphatic Hydrocarbon fine particle dispersion was obtained. The volume-based median diameter of the aliphatic hydrocarbon fine particles was measured using a dynamic light scattering type particle size distribution analyzer (Nanotrac: manufactured by Nikkiso Co., Ltd.) and was 0.15 μm.

<Manufacture of silicone oil emulsion>
-20.0 parts of silicone oil (Dimethyl silicone oil Shin-Etsu Chemical Co., Ltd .: KF 96-50 CS)
・ Anion surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 part ・ Ion-exchanged water 79.0 parts Mix the above and use high pressure impact type dispersing machine Nanomizer (Yoshida Kakogyo Co., Ltd.) for about 1 hour An aqueous emulsion having a concentration of 20% of silicone oil dispersed was prepared by dispersing the silicone oil. The volume-based median diameter of silicone oil particles in the obtained silicone oil emulsion was measured using a dynamic light scattering type particle size distribution analyzer (Nanotrac: manufactured by Nikkiso Co., Ltd.) and was 0.09 μm.

Example 1
Resin fine particle 1 dispersion 500 parts Colorant fine particle dispersion 80 parts Aliphatic hydrocarbon fine particle dispersion 150 parts Silicone oil emulsion 50 parts Ion exchanged water 160 parts Each of the above materials in a round stainless steel flask After charging and mixing, 60 parts of a 10% aqueous solution of magnesium sulfate was added. Subsequently, dispersion was carried out at 5000 rpm for 10 minutes using a homogenizer (manufactured by IKA: Ultra-Turrax T50). Thereafter, using a stirring blade in a heating water bath, the mixture was heated to 73 ° C. while appropriately adjusting the number of revolutions such that the mixture was stirred. After holding at 73 ° C. for 20 minutes, it was confirmed that the volume-based median diameter of the formed aggregate particles was about 6.0 μm.
After 330 parts of a 5% aqueous solution of ethylenediaminetetraacetic acid in water was added to the dispersion containing the above-mentioned aggregate particles, the mixture was heated to 98 ° C. while continuing the stirring. Then, the aggregate particles were fused by holding at 98 ° C. for 1 hour.
After that, cooling to 50 ° C. and holding for 3 hours promoted crystallization of the ethylene-vinyl acetate copolymer. After cooling to 25 ° C., and filtering and solid-liquid separation, the filtrate was washed with a 0.5% aqueous solution of ethylenediaminetetraacetic acid sodium acetate, and then washed with ion-exchanged water.
After washing, the resultant was dried using a vacuum drier to obtain toner particles having a volume-based median diameter of 5.4 μm.
With respect to 100 parts of the obtained toner particles, 1.5 parts of hydrophobized silica fine particles having a number average particle size of 10 nm of primary particles and a hydrophobized process of having a number average particle size of 100 nm Toner was obtained by dry mixing 2.5 parts of the fine silica particles with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The constitution conditions of the obtained toner are shown in Table 1.

Example 2
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 2. The volume based median diameter of the obtained toner particles was 5.3 μm.

Example 3
A toner was obtained in the same manner as Example 1, except that resin fine particles 1 were changed to resin fine particles 3. The volume based median diameter of the obtained toner particles was 5.3 μm.

Example 4
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 4. The volume-based median diameter of the obtained toner particles was 5.2 μm.

Example 5
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 5. The volume based median diameter of the obtained toner particles was 5.5 μm.

Example 6
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 6. The volume-based median diameter of the obtained toner particles was 5.2 μm.

Example 7
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 7. The volume-based median diameter of the obtained toner particles was 5.1 μm.

Example 8
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 8. The volume based median diameter of the obtained toner particles was 5.4 μm.

Example 9
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 9. The volume-based median diameter of the obtained toner particles was 5.2 μm.

Example 10
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 10. The volume-based median diameter of the obtained toner particles was 5.6 μm.

Example 11
A toner was obtained in the same manner as in Example 1 except that the amount of the aliphatic hydrocarbon fine particle dispersion was 50 parts. The volume-based median diameter of the obtained toner particles was 5.2 μm.

Example 12
A toner was obtained in the same manner as in Example 1, except that the amount of the aliphatic hydrocarbon fine particle dispersion was 100 parts. The volume-based median diameter of the obtained toner particles was 5.1 μm.

Example 13
A toner was obtained in the same manner as Example 1 except that the silicone oil emulsion was not added. The volume-based median diameter of the obtained toner particles was 5.2 μm.

Example 14
A toner was obtained in the same manner as in Example 1, except that 500 parts of resin fine particle 1 dispersion liquid was changed to 375 parts of resin fine particle 1 dispersion liquid and 125 parts of resin fine particle 29 dispersion liquid. The volume-based median diameter of the obtained toner particles was 6.1 μm.

Example 15
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 11. The volume-based median diameter of the obtained toner particles was 5.2 μm.

Example 16
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 12. The volume based median diameter of the obtained toner particles was 5.5 μm.

Example 17
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 13. The volume-based median diameter of the obtained toner particles was 5.1 μm.

Example 18
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 14. The volume-based median diameter of the obtained toner particles was 5.1 μm.

Example 19
A toner was obtained in the same manner as in Example 1, except that 500 parts of resin fine particle 1 dispersion liquid was changed to 250 parts of resin fine particle 1 dispersion liquid and 250 parts of resin fine particle 11 dispersion liquid. The volume-based median diameter of the obtained toner particles was 5.0 μm.

Example 20
A toner was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to the resin fine particles 15. The volume-based median diameter of the obtained toner particles was 5.2 μm.

Example 21
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 16. The volume-based median diameter of the obtained toner particles was 5.2 μm.

Example 22
A toner was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to the resin fine particles 17. The volume based median diameter of the obtained toner particles was 5.3 μm.

Example 23
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 18. The volume-based median diameter of the obtained toner particles was 5.2 μm.

Comparative Example 1
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 19. The volume-based median diameter of the obtained toner particles was 5.1 μm.

Comparative Example 2
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 20. The volume based median diameter of the obtained toner particles was 5.3 μm.

Comparative Example 3
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 21. The volume based median diameter of the obtained toner particles was 5.5 μm.

Comparative Example 4
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 22. The volume based median diameter of the obtained toner particles was 5.4 μm.

Comparative Example 5
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 23. The volume based median diameter of the obtained toner particles was 6.8 μm.

Comparative Example 6
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 24. The volume-based median diameter of the obtained toner particles was 10.3 μm.

Comparative Example 7
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 25. The volume-based median diameter of the obtained toner particles was 11.0 μm.

Comparative Example 8
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 26. The volume-based median diameter of the obtained toner particles was 5.0 μm.

Comparative Example 9
A toner was obtained in the same manner as in Example 1 except that the resin fine particle 1 was changed to the resin fine particle 27. The volume-based median diameter of the obtained toner particles was 5.1 μm.

Comparative Example 10
A toner was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to the resin fine particles 28. The volume based median diameter of the obtained toner particles was 5.8 μm.

Comparative Example 11
The resin fine particle 1 is used as the resin fine particle 29, the addition amount of the aliphatic hydrocarbon fine particle dispersion is 50 parts, the silicone oil emulsion is not used, and the temperature for forming the aggregate particle is 60 ° C. In the same manner as in Example 1, a toner was obtained. The volume based median diameter of the obtained toner particles was 5.4 μm.

Comparative Example 12
The resin fine particle 1 is used as the resin fine particle 30, the addition amount of the aliphatic hydrocarbon fine particle dispersion is 50 parts, the silicone oil emulsion is not used, and the temperature for forming the aggregate particles is 60 ° C. In the same manner as in Example 1, a toner was obtained. The volume based median diameter of the obtained toner particles was 5.4 μm.

The following evaluation test was performed using each of the above toners. The evaluation results are shown in Table 2.
<Evaluation of storage stability (blocking resistance)>
The toner was allowed to stand for 3 days in a constant temperature and humidity chamber with a temperature of 50 ° C. and a humidity of 50% RH, and the degree of blocking was evaluated visually.
A: Blocking does not occur, or even if it occurs, it disperses easily by light vibration.
B: Blocking occurs, but disperses as it continues vibrating.
C: Blocking occurs and does not disperse even if force is applied.

<Evaluation of high humidity storage stability>
The toner was allowed to stand in a constant temperature and humidity chamber with a temperature of 40 ° C. and a humidity of 95% RH for 30 days, and the degree of blocking was evaluated visually.
A: Blocking does not occur, or even if it occurs, it disperses easily by light vibration.
B: Blocking occurs, but disperses as it continues vibrating.
C: Blocking occurs and does not disperse even if force is applied.

<Evaluation of low temperature fixability>
The toner and a ferrite carrier (average particle diameter 42 μm) surface-coated with a silicone resin were mixed so that the concentration of the toner was 8% by mass, to prepare a two-component developer.
An unfixed toner image (0.6 mg / cm ² ) was formed on an image receiving paper (64 g / m ² ) using a commercially available full color digital copier (CLC 1100, manufactured by Canon Inc.).
A fixing unit removed from a commercially available full color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon Inc.) was modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using this.
The process speed was set to 246 mm / sec under normal temperature and normal humidity, and the condition when the unfixed image was fixed was visually evaluated.
A: Fixing is possible at a temperature of 110 ° C. or less.
B: Fixing is possible at temperatures higher than 110 ° C. and lower than 130 ° C.
C: Fixing is possible at a temperature higher than 130 ° C., or there is no temperature range that can be fixed.

<Evaluation of eraser resistance>
The toner image was fixed in the same manner as in "Evaluation of low temperature fixability".
Then, with respect to the fixed material at the maximum fixing temperature, the erase resistance was tested at a load of 300 g using an eraser (product name: MONO, manufactured by Dragonfly Pencil Co., Ltd.).
The maximum fixing temperature is fixed while raising the roller temperature by 10 ° C. from the lowest fixing temperature to 200 ° C. using the above measurement method, and is taken as the maximum temperature at which hot offset does not occur.
The occurrence of the hot offset was judged by visually observing the presence or absence of toner adhesion to the fixing roller.
A: Not erased by the eraser.
B: The image density is reduced by erasing with an eraser.
C: Erased by an eraser.

<Evaluation of charge retention>
0.01 g of toner was weighed into an aluminum pan and charged to -600 V using a Strocolon charging device. Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface voltmeter (model 347 manufactured by Trek Japan) under an atmosphere of temperature 30 ° C. and humidity 80% RH.
From the measured results, the charge retention rate was calculated by the following equation. The charge retention was evaluated based on the charge retention.
Charge retention after 30 minutes (%) = (surface potential after 30 minutes / initial surface potential) × 100
A: charge retention rate is 90% or more B: charge retention rate is 50% or more and less than 90% C: charge retention rate is 10% or more and less than 50% D: charge retention rate is less than 10%

表中、
Ｙ２は、エステル基含有オレフィン系共重合体Ａ中の構造Ｙ２の含有量（質量％）を表す。
Ｚ３は、酸基及びエステル基含有オレフィン系共重合体Ｂ中の構造Ｚ３の含有量（質量％）を表す。
Ｍは、メルトフローレート（単位：ｇ／１０分）を表す。
含有量（１）は、樹脂成分中のエステル基含有オレフィン系共重合体Ａの含有量（質量％）を表す。
含有量（２）は、樹脂成分中の酸基及びエステル基含有オレフィン系共重合体Ｂの含有量（質量％）を表す。
含有量（３）は、樹脂成分１００質量部に対する、脂肪族炭化水素化合物の含有量（質量部）を表す。
含有量（４）は、樹脂成分１００質量部に対する、シリコーンオイルの含有量（質量部）を表す。
酸価の単位は、“ｍｇＫＯＨ／ｇ”である。

In the table,
Y2 represents the content (% by mass) of the structure Y2 in the ester group-containing olefin copolymer A.
Z3 represents the content (% by mass) of the structure Z3 in the acid group- and ester group-containing olefin copolymer B.
M represents a melt flow rate (unit: g / 10 min).
Content (1) represents the content (% by mass) of the ester group-containing olefin copolymer A in the resin component.
The content (2) represents the content (% by mass) of the acid group- and ester group-containing olefin copolymer B in the resin component.
Content (3) represents the content (parts by mass) of the aliphatic hydrocarbon compound with respect to 100 parts by mass of the resin component.
Content (4) represents the content (parts by mass) of silicone oil with respect to 100 parts by mass of the resin component.
The unit of the acid value is "mg KOH / g".

Claims (11)

A toner having toner particles containing a resin component,
The resin component contains an ester group-containing olefin copolymer A, and an acid group and an ester group-containing olefin copolymer B,
The acid value of the olefin copolymer A is 0 mg KOH / g or more and 10 mg KOH / g or less,
The acid value of the olefin copolymer B is 50 mg KOH / g or more and 250 mg KOH / g or less,
The olefin copolymer A is
A structure Y1 represented by the following formula (1),
And at least one structure Y2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3),
The content of the structure Y2 in the olefin copolymer A is 3% by mass or more and 35% by mass or less,
The olefin copolymer B is
A structure Z1 represented by the following formula (4),
A structure Z2 represented by the following formula (5),
And at least one structure Z3 selected from the group consisting of a structure represented by the following formula (6) and a structure represented by the following formula (7):
The content of the structure Z3 in the olefin copolymer B is 1% by mass or more and 20% by mass or less,
A toner, wherein the content of the olefin copolymer A in the resin component is 50% by mass or more.

(In the formulas (1) to (7), R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , and R ⁴ represents H or indicates CH _3, ^{R 5} represents a CH ₃ or _C 2 _{H 5,} ^{R 6} represents H or CH _3, ^{R 7} represents H or CH _3, ^{R 8} represents H or CH _3, ^{R 9} Represents CH ₃ , C ₂ H ₅ , C ₃ H ₇ or C ₄ H ₉ , R ¹⁰ represents H or CH ₃ , R ¹¹ represents CH ₃ , C ₂ H ₅ , C ₃ H ₇ or C ₄ H ₉ )) Let the total mass of the olefin copolymer A be W,
Let l be the mass of the structure represented by the formula (1),
Let m be the mass of the structure represented by the formula (2),
When the mass of the structure represented by the formula (3) is n,
The toner according to claim 1, wherein the value of (l + m + n) / W in the olefin copolymer A is 0.80 or more.   The toner according to claim 1, wherein a content of the olefin copolymer B in the resin component is 10% by mass or more and less than 50% by mass.   The toner according to any one of claims 1 to 3, wherein the melt flow rate of the olefin copolymer A is 5 g / 10 minutes to 30 g / 10 minutes.   The toner according to any one of claims 1 to 4, wherein a content of the structure Z3 in the olefin copolymer B is 5% by mass or more and 10% by mass or less. The toner particles contain an aliphatic hydrocarbon compound,
The melting point of the aliphatic hydrocarbon compound is 50 ° C. or more and 100 ° C. or less,
The toner according to any one of claims 1 to 5, wherein a content of the aliphatic hydrocarbon compound is 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin component.   The toner according to any one of claims 1 to 6, wherein a content of the structure Y2 in the olefin copolymer A is 5% by mass or more and 20% by mass or less. The toner particles contain silicone oil,
The toner according to any one of claims 1 to 7, wherein a content of the silicone oil is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component. A toner having toner particles containing a resin component,
The resin component is
An ethylene-vinyl acetate copolymer having an acid value of 0 mg KOH / g to 10 mg KOH / g,
And at least one of an ethylene-vinyl acetate-acrylic acid copolymer and an ethylene-vinyl acetate-methacrylic acid copolymer, having an acid value of 50 mgKOH / g or more and 250 mgKOH / g or less,
The content of the ethylene-vinyl acetate copolymer in the resin component is 50% by mass or more,
The content of vinyl acetate-derived monomer units in the ethylene-vinyl acetate copolymer is 3% by mass or more and 35% by mass or less,
The content of monomer units derived from vinyl acetate in at least one of the ethylene-vinyl acetate-acrylic acid copolymer and the ethylene-vinyl acetate-methacrylic acid copolymer is 1% by mass or more and 20% by mass or less Toner characterized by A method for producing a toner having toner particles containing a resin component, comprising:
The resin component contains an ester group-containing olefin copolymer A, and an acid group and an ester group-containing olefin copolymer B,
Preparing a fine resin particle dispersion, wherein fine resin particles for producing the resin component are dispersed in an aqueous medium,
Aggregating the resin fine particles to form aggregate particles, and
Heating the aggregate particles to fuse them,
The acid value of the olefin copolymer A is 0 mg KOH / g or more and 10 mg KOH / g or less,
The acid value of the olefin copolymer B is 50 mg KOH / g or more and 250 mg KOH / g or less,
The olefin copolymer A is
A structure Y1 represented by the following formula (1),
And at least one structure Y2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3),
The content of the structure Y2 in the olefin copolymer A is 3% by mass or more and 35% by mass or less,
The olefin copolymer B is
A structure Z1 represented by the following formula (4),
A structure Z2 represented by the following formula (5),
And at least one structure Z3 selected from the group consisting of a structure represented by the following formula (6) and a structure represented by the following formula (7):
The content of the structure Z3 in the olefin copolymer B is 1% by mass or more and 20% by mass or less,
The method for producing a toner, wherein the content of the olefin copolymer A in the resin component is 50% by mass or more.

(In the formulas (1) to (7), R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , and R ⁴ represents H or indicates CH _3, ^{R 5} represents a CH ₃ or _C 2 _{H 5,} ^{R 6} represents H or CH _3, ^{R 7} represents H or CH _3, ^{R 8} represents H or CH _3, ^{R 9} Represents CH ₃ , C ₂ H ₅ , C ₃ H ₇ or C ₄ H ₉ , R ¹⁰ represents H or CH ₃ , R ¹¹ represents CH ₃ , C ₂ H ₅ , C ₃ H ₇ or C ₄ H ₉ )) A method for producing a toner having toner particles containing a resin component, comprising:
Preparing a fine resin particle dispersion, wherein fine resin particles for producing the resin component are dispersed in an aqueous medium,
Aggregating the resin fine particles to form aggregate particles, and
Heating the aggregate particles to fuse them,
The resin component is
An ethylene-vinyl acetate copolymer having an acid value of 0 mg KOH / g to 10 mg KOH / g,
At least one copolymer selected from the group consisting of an ethylene-vinyl acetate-acrylic acid copolymer and an ethylene-vinyl acetate-methacrylic acid copolymer, having an acid value of 50 mg KOH / g or more and 250 mg KOH / g or less Contains
The content of the ethylene-vinyl acetate copolymer in the resin component is 50% by mass or more,
The content of vinyl acetate-derived monomer units in the ethylene-vinyl acetate copolymer is 3% by mass or more and 35% by mass or less,
The content of monomer units derived from vinyl acetate in at least one copolymer selected from the group consisting of ethylene-vinyl acetate-acrylic acid copolymer and ethylene-vinyl acetate-methacrylic acid copolymer is 1 A method for producing a toner, comprising: mass% to 20 mass%.