JP7242217B2 - Toner and toner manufacturing method - Google Patents

Description

The present invention relates to a toner used in electrophotography, electrostatic recording, electrostatic printing, and the like, and a method for producing the toner.

In recent years, with the widespread use of electrophotographic full-color copiers, not only is there a need for higher speeds and higher image quality, but there are added values that improve serviceability such as maintenance costs, such as color stability and maintenance-free performance. Improvements are also required.
Specifically, a toner that does not easily deteriorate even in long-term image output is required as a toner that realizes improvement in maintenance performance.
Therefore, as a toner that does not easily deteriorate even in long-term image output, a proposal has been made to add inorganic fine particles having a large particle size to the toner surface to develop a spacer effect (Patent Document 1). Also, a proposal has been made to use a thermoplastic elastomer resin, which is a resin having rubber elasticity and a low glass transition temperature (Patent Document 2).

JP 2012-063607 A JP 2011-128410 A

With the toner described in Patent Document 1, in the initial image output, the adhesive force of the toner is reduced due to the spacer effect caused by the inorganic fine particles, so it is possible to output high-quality images with good developability and transferability. It's becoming
However, since the toner described in Patent Document 1 uses polyester or styrene-acrylic resin as the binding resin, large-sized non-microscopic particles are buried in the toner surface due to agitation of the developing device during long-term image output. It may happen. As a result, the spacer effect is reduced and the adhesion of the toner is increased, so that the transfer efficiency is lowered and the image density may be lowered. In other words, in long-term image output, maintenance such as replacement of the developer may be required.
On the other hand, the toner described in Japanese Patent Application Laid-Open No. 2002-200001 suppresses the burial of the inorganic fine particles due to rubber elasticity even during long-term image output, and maintains the reduction in toner adhesion force. However, due to its high rubber elasticity, the inorganic fine particles adhering to the toner surface are likely to be detached, and the inorganic fine particles may contaminate the toner carrying member (carrier) of the two-component developer and the charging member. As a result, charging stability is lowered, resulting in image defects and vertical streaks on the paper surface, which may require maintenance such as replacement of the developer and charging member.
From the above, there is a trade-off relationship between the suppression of embedding and the suppression of detachment of inorganic fine particles. Development of a toner that can break away from this trade-off relationship and maintain excellent transfer performance and charging stability in long-term image output. is urgent.

The toner of the present invention is a toner having toner particles and inorganic fine particles,
The resin present on the surface of the toner particles has a displacement h of 300 nm to 500 nm when a load of 50 μN is applied in an environment of 25° C., as measured by an ultra-microhardness measuring device, and is plastically deformed. The rate H is 1.0% to 30.0%,
The inorganic fine particles have a rectangular parallelepiped particle shape,
the inorganic fine particles are strontium titanate,
The resin present on the surface of the toner particles contains 50% by mass or more of an ester group-containing olefin copolymer,
The ester group-containing olefinic copolymer has an ester group concentration of 2.0% by mass to 17.9% by mass based on the total mass of the ester group-containing olefinic copolymer.

A method for producing a toner of the present invention is a method for producing a toner of the present invention, comprising:
The manufacturing method is
a dispersion step of adjusting the resin fine particle dispersion;
an aggregating step of aggregating the resin fine particle dispersion to form an aggregate; and
It is characterized by having a fusion step of heating and fusing the aggregate.

By using the toner of the present invention, it is possible to provide a toner that maintains excellent transferability and charging stability in long-term image output.

It is an example of the measurement result of the displacement of the resin measured by the ultra-microhardness measuring device.

In the present invention, unless otherwise specified, the descriptions of "○○ or more and XX or less" and "○○ to XX", which represent numerical ranges, mean numerical ranges including the lower and upper limits that are endpoints.

The toner of the present invention is a toner having toner particles and inorganic fine particles,
The resin present on the surface of the toner particles has a displacement h of 300 nm to 500 nm when a load of 50 μN is applied in an environment of 25° C., as measured by an ultra-microhardness measuring device, and is plastically deformed. The rate H is 1.0% to 30.0%,
The inorganic fine particles are characterized by having a rectangular parallelepiped particle shape.
Here, the reason why the displacement h and the plastic deformation rate H when a load of 50 μN is applied in an environment of 25° C. measured by an ultra-microhardness measuring device is specified because one toner particle in the developing device of the actual machine This is based on the fact that the maximum load applied to is 50 μN, which is derived from a simulation or the like.

The surface of a toner particle refers to a region of 0 nm to 100 nm from the outer surface of the toner particle toward the center (midpoint of the long axis) in cross-sectional observation of the toner using a transmission electron microscope (TEM). The inside of the toner particle refers to a region inside 100 nm from the outer surface of the toner particle toward the center (middle point of the long axis) in cross-sectional observation of the toner using a transmission electron microscope (TEM).

As for the toner particles, it is sufficient that the resin present on the surfaces thereof has the mechanical properties described below. The toner particles may have a core-shell structure in which the surface is a shell layer, or the toner particle surface and the toner particle interior may contain a resin having similar mechanical properties.
The state of existence of the resin present on the surface of the toner particles is controlled, for example, by appropriately changing the mass ratio of the core particles and the shell particles, the reaction time, the reaction temperature, etc. in the core-shell formation using the emulsion aggregation method described below. be able to.
As a method for controlling the state of existence of the resin existing on the surface of the toner particles other than the emulsion aggregation method, for example, a mixture of the toner constituent materials described below dissolved or dispersed in a water-insoluble organic solvent is dispersed in an aqueous medium. A “dissolution suspension method” in which toner particles are granulated using a In the dissolution suspension method, the affinity between a resin having mechanical properties described below and an aqueous medium is increased, specifically, by increasing the solubility parameter described below, the resin is spontaneously formed into toner particles. can be localized on the surface of

When the displacement h of the resin when a load of 50 μN is applied in an environment of 25° C. measured by an ultra-microhardness measuring device is 300 nm to 500 nm, the resin acts as a cushioning material, so the toner is The resin can absorb the load applied to one particle, and the embedding of the inorganic fine particles in the toner particles can be suppressed, thereby improving transferability. The displacement h is preferably between 350 nm and 490 nm, more preferably between 400 nm and 480 nm.
On the other hand, when the displacement h is less than 300 nm, the displacement when the maximum load received in the developing machine is applied is small, so the load applied to one toner particle cannot be sufficiently absorbed, and the inorganic fine particles tend to be buried. , the transferability decreases. Further, when the displacement h is larger than 500 nm, the melting point of the resin is lowered due to the material design of the resin. Therefore, the resin is likely to melt and deform during long-term image output under a high-temperature and high-humidity environment, and the inorganic fine particles are likely to be buried. , resulting in a decrease in transferability.
The displacement h can be adjusted by appropriately changing the ester group concentration and the molecular weight of the resin present on the surface of the toner particles, which will be described later.

When the plastic deformation rate H of the resin is 1.0% to 30.0% when a load of 50 μN is applied in an environment of 25° C., measured by an ultra-microhardness measuring device, the toner particles This means that the resin present on the surface is resistant to plastic deformation even when the maximum load received in the developing machine is applied, that is, it has rubber elasticity. As a result, the burial of the inorganic fine particles can be suppressed, so that the spacer effect can be exhibited even in long-term image output. As a result, transferability is improved. The plastic deformation rate H is preferably 1.0% to 20.0%, more preferably 1.0% to 15.0%.
On the other hand, when the plastic deformation rate H is less than 1.0%, the melting point of the resin is lowered due to the material design of the resin. Fine particles are likely to be buried, resulting in a decrease in transferability. On the other hand, if the plastic deformation rate H is more than 30.0%, sufficient rubber elasticity that can suppress the embedding of the inorganic fine particles is not exhibited, so that the inorganic fine particles are likely to be buried, resulting in poor transferability.
The plastic deformation rate H can be adjusted by appropriately changing the ester group concentration and the molecular weight of the resin present on the surface of the toner particles, which will be described later.

As a result of intensive studies by the present inventors, the toner particles having the resin present on the surface can suppress embedding of the inorganic fine particles added to the toner particles due to the viscoelastic properties of the resin. It has been found that the inorganic fine particles are more likely to be detached from the toner particles than the toner having a resin on the surface.
That is, only by appropriately controlling the viscoelasticity of the resin present on the surface of the toner particles, there is a trade-off relationship between the suppression of embedding and the suppression of detachment of the inorganic fine particles. Therefore, there is room for improvement to a toner that overcomes this trade-off relationship and can maintain excellent transferability and charging stability in long-term image output.

Therefore, the present inventors focused on not only the viscoelastic properties of the resin present on the surface of the toner particles, but also the shape of the inorganic fine particles. As a result, the inventors have found that when the inorganic fine particles have a rectangular parallelepiped particle shape, the inorganic fine particles are difficult to separate from the toner particles in the toner in which the resin is present on the surface of the toner particles.
This is because the inorganic fine particles have a rectangular parallelepiped particle shape, so that the contact area between the toner particles and the inorganic fine particles is larger than that of the spherical fine particles, so that the coefficient of friction between the toner particle surface and the inorganic fine particle surface increases. It is thought that this is because the resistance to detachment is greatly increased.

The inorganic fine particles have a rectangular parallelepiped particle shape. If the particles have a rectangular parallelepiped particle shape, for example, in the step of attaching the inorganic fine particles to the toner particles, the inorganic fine particles are likely to adhere to the toner particles, so that the fixing rate of the inorganic fine particles is further improved. The inorganic fine particles preferably have a cubic particle shape among rectangular parallelepiped particle shapes.
The cubic shape and rectangular parallelepiped shape are not limited to perfect cubes and rectangular parallelepipeds, respectively, and include, for example, substantially cubic and substantially rectangular parallelepiped shapes with partially missing or rounded corners.
Further, the aspect ratio of the inorganic fine particles having a rectangular parallelepiped particle shape is preferably 1.0 to 3.0.

The inorganic fine particles are not particularly limited as long as they have a rectangular parallelepiped particle shape, but titanate is preferable because it is easy to control the cubic particle shape. Specific examples of titanates include barium titanate, aluminum titanate, magnesium titanate, calcium titanate, and strontium titanate. Among them, strontium titanate is preferably used, and strontium titanate having a perovskite crystal structure is more preferably used.

Strontium titanate having a rectangular parallelepiped particle shape and a perovskite crystal structure can be produced mainly in an aqueous medium without going through a sintering process. Production in an aqueous medium is preferable because it is easy to control the particles to have a uniform particle size.
That is, strontium titanate, which has a rectangular parallelepiped particle shape and a perovskite-type crystal structure, stays on the toner particle surface in a state in which it is difficult to detach from toner particles in which a resin having rubber elasticity exists on the toner particle surface. is possible. The toner particles have rubber elasticity as described above, and have higher tackiness than the amorphous resins conventionally used in toners. It expresses a very high coefficient of friction. As a result, the inorganic fine particles are less likely to be detached from the surface of the toner particles, and are less likely to be buried inside the toner particles due to the rubber elasticity of the resin even when subjected to mechanical stress. Therefore, excellent transferability and charging stability can be maintained in long-term image output.

The strontium titanate can be obtained, for example, by an atmospheric heating reaction method. The normal pressure heating reaction method will be described below, but the method is not limited to this method.
In the production of strontium titanate by the normal pressure heating reaction method, a mineral acid peptization product of a hydrolyzate of a titanium compound can be used as a titanium oxide source. As the mineral acid deflocculated product, metatitanic acid obtained by the sulfuric acid method and peptized by adjusting the pH to 0.8 to 1.5 with hydrochloric acid can be preferably used. The SO ₃ content in metatitanic acid is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, from the viewpoint of promoting efficient deflocculation.
As the strontium oxide source, metal nitrates, hydrochlorides and the like can be used, for example, strontium nitrate, strontium chloride and the like can be used. Strontium titanate can be produced by mixing respective solutions containing titanium or strontium, reacting the mixture while adding an alkaline aqueous solution at 60° C. or higher, and then acid-treating the mixture.
As the alkaline aqueous solution, caustic alkali can be used, and sodium hydroxide aqueous solution is particularly preferable.
In the production method described above, factors affecting the particle size of the obtained strontium titanate include, for example, the mixing ratio of the titanium oxide source and the strontium oxide source during the reaction, the concentration of the titanium oxide source at the initial stage of the reaction, and the addition of an alkaline aqueous solution. temperature and addition rate when
In addition, in order to prevent the formation of carbonate during the reaction process, it is preferable to prevent contamination with carbon dioxide, such as by performing the reaction in a nitrogen gas atmosphere.

The mixing ratio of the titanium oxide source and the strontium oxide source during the reaction is preferably 0.90 to 1.40, more preferably 1.05 to 1.20, in terms of SrO/TiO ₂ molar ratio. The concentration of the titanium oxide source at the initial stage of the reaction is preferably 0.05 mol/L to 1.30 mol/L, more preferably 0.08 mol/L to 1.00 mol/L as TiO ₂ .
The temperature at which the alkaline aqueous solution is added can be practically within the range of 60°C to 100°C, because if the temperature exceeds 100°C, a pressure vessel such as an autoclave is required. As for the addition rate of the alkaline aqueous solution, the slower the addition rate, the larger the metal titanate particles can be obtained, and the faster the addition rate, the smaller the particle size of the metal titanate particles can be obtained. The addition rate of the alkaline aqueous solution is preferably 0.001 equivalents/h to 1.200 equivalents/h, more preferably 0.002 equivalents/h to 1.100 equivalents/h, relative to the feedstock.
After the strontium titanate particles are obtained by the normal pressure heating reaction, they are preferably further acid-treated in order to remove unreacted metal sources.
In the acid treatment, hydrochloric acid can be used to adjust the pH to preferably 2.5 to 7.0, more preferably 4.5 to 6.0. As an acid, besides hydrochloric acid, nitric acid, acetic acid, or the like can be used for the acid treatment.

<Surface potential B>
The surface potential B is preferably 100 V or higher, more preferably 150 V to 400 V, when a rubbing test is performed using the inorganic fine particles and the resin present on the surface of the toner particles. When the surface potential B is within the above range, the charging stability of the toner is further improved.
The surface potential B can be controlled, for example, by appropriately changing the surface treatment agent when the inorganic fine particles are surface-treated. When the surface potential B is in the range of 100 V or higher, separation of the inorganic fine particles from the toner particle surface is further suppressed, and as a result, transferability is further improved.

The inorganic fine particles may be surface-treated with a surface treatment agent. Although the surface treatment agent is not particularly limited, examples thereof include disilylamine compounds, halogenated silane compounds, silicone compounds and silane coupling agents.
A disilylamine compound is a compound having a disilylamine (Si—N—Si) moiety. Examples of disilylamine compounds include, for example, hexamethyldisilazane (HMDS), N-methyl-hexamethyldisilazane and hexamethyl-N-propyldisilazane. Examples of halogenated silane compounds include, for example, dimethyldichlorosilane.
Examples of silicone compounds include silicone oil and silicone resin (varnish). Examples of silicone oils include dimethylsilicone oil, methylphenylsilicone oil, α-methylstyrene-modified silicone oil, chlorophenylsilicone oil and fluorine-modified silicone oil. Examples of silicone resins (varnishes) include methylsilicone varnish and phenylmethylsilicone varnish.
Examples of silane coupling agents include silane coupling agents having an alkyl group and an alkoxy group, silane coupling agents having an amino group and an alkoxy group, and fluorine-containing silane coupling agents. More specifically, the silane coupling agent includes, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, trimethylmethoxysilane, trimethyldiethoxysilane, triethylmethoxysilane, triethyldiethoxysilane, γ - glycidoxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxymethylsilane or γ-aminopropyldiethoxymethylsilane , 3,3,3-trifluoropropyldimethoxysilane, 3,3,3-trifluoropropyldiethoxysilane, perfluorooctylethyltriethoxysilane, and 1,1.1-trifluorohexyldiethoxysilane, etc. mentioned.
The surface treatment agents may be used singly or in combination of two or more.

<Solubility parameter (SP value)>
In the toner particles, the solubility parameter (SP1) of the resin present on the surface of the toner particles and the solubility parameter (SP2) of the surface treatment agent used for the inorganic fine particles preferably satisfy the following formula (1), and the following formula ( 1′) is more preferably satisfied.
|SP1−SP2|≦1.00 (1)
0.03≦|SP1−SP2|≦0.85 (1′)
The above SP values (SP1 and SP2) can be obtained using the Fedors formula. Here, the values of Δei and Δvi are the vaporization energies and molar volumes ( 25°C).
Formula: δi=[Ev/V] ^1/2 =[Δei/Δvi] ^1/2
Ev: evaporation energy V: molar volume Δei: evaporation energy of i component atom or atomic group Δvi: molar volume of i component atom or atomic group

For example, the SP value of a resin composed of ethylene and norbornene and having a copolymerization ratio of 1:1 is composed of atomic groups (-5 or more-membered ring structures) x 1 + (-CH ₂ ) x 3 as repeating units. , the SP value is obtained by the following formula.
δi=[Δei/Δvi] ^1/2 =[{(250)×1+(1180)×3}/{(16)×1+(16.1)×3}] ^1/2
Therefore, the SP value (δi) is 7.43.
By setting |SP1-SP2| to 1.00 or less, the chemical affinity between the surface of the inorganic fine particles and the surface of the toner particles is further improved. As a result, detachment of the inorganic fine particles from the surfaces of the toner particles can be further suppressed.

<Addition amount of inorganic fine particles>
From the viewpoint of charging stability, the inorganic fine particles having a rectangular parallelepiped particle shape are preferably used in an amount of 0.1 to 20.0 parts by mass, more preferably 0.1 part by mass, per 100 parts by mass of the toner particles. parts by mass to 15.0 parts by mass.

<Particle size of inorganic fine particles>
The number average particle diameter of the primary particles of the inorganic fine particles having a rectangular parallelepiped particle shape is preferably 10 nm to 250 nm. When the particle size is 250 nm or less, separation from the surface of the toner particles can be suppressed when the toner particles and the inorganic fine particles are mixed in the toner production. When the particle diameter is 10 nm or more, a spacer effect is exhibited by the inorganic fine particles, so transferability is improved. Among them, the thickness is more preferably 20 to 100 nm, further preferably 30 to 100 nm, from the viewpoint of allowing the inorganic fine particles to adhere more uniformly and more firmly.

In addition to the above-mentioned inorganic fine particles having a rectangular parallelepiped particle shape, the toner particles may contain other inorganic fine powders, if necessary. The inorganic fine powder may be added internally to the toner particles, or may be mixed with the toner particles as an external additive.
As the external additive, inorganic fine powders such as silica, titanium oxide and aluminum oxide are preferred. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil and mixtures thereof.
As an external additive for improving fluidity, inorganic fine powder having a specific surface area of 50 m ² /g to 400 m ² /g is preferable, and as an external additive for durability stability, a specific surface area of 10 m ² /g is preferable. An inorganic fine powder having a density of 50 m ² /g or more is preferable. In order to improve fluidity and stabilize durability, an inorganic fine powder having a specific surface area within the above range may be used in combination.
The external additive is preferably used in an amount of 0.1 to 10.0 parts by mass with respect to 100 parts by mass of toner particles. A known mixer such as a Henschel mixer can be used to mix the toner particles and the external additive.

For mixing the toner particles and the inorganic fine particles, known mixers such as Henschel Mixer, Mechanohybrid (manufactured by Nippon Coke Co., Ltd.), Super Mixer, and Nobilta (manufactured by Hosokawa Micron Corporation) can be used, and are not particularly limited. do not have.

<Resin Present on Surface of Toner Particle>
The resin present on the surface of the toner particles preferably contains 50% by mass or more of the ester group-containing olefin copolymer, more preferably more than 50% by mass, and 70% by mass to 100% by mass. It is more preferable to contain the mass %. As a result, the resin existing on the surface of the toner particles exhibits appropriate rubber elasticity, and excellent transferability can be maintained in long-term image output.
Further, when the resin existing on the surface of the toner particles contains 50% by mass or more of the ester group-containing olefin copolymer, the main component of the resin existing on the surface of the toner particles is an elastomer resin having a low glass transition temperature. Therefore, the resin existing on the surface of the toner particles can easily act as a cushioning agent, and burying of the inorganic fine particles can be further suppressed.

Further, the ester group-containing olefinic copolymer is selected from the group consisting of a unit Y1 represented by the following formula (2), a unit represented by the following formula (3), and a unit represented by the following formula (4). and at least one type of unit Y2. In this case, the resin existing on the surface of the toner particles tends to exhibit rubber elasticity, and excellent transferability can be maintained in long-term image output.
Further, in the above case, the main component of the resin present on the surface of the toner particles is an elastomer resin having a low glass transition temperature. can be further suppressed.

（式中、Ｒ^１はＨまたはＣＨ_３を示し、Ｒ^２はＨまたはＣＨ_３を示し、Ｒ^３はＣＨ_３またはＣ_２Ｈ_５を示し、Ｒ^４はＨまたはＣＨ_３を示し、Ｒ^５はＣＨ_３またはＣ_２Ｈ_５を示す。）

(wherein R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , R ⁴ represents H or CH ₃ , R ⁵ represents indicates _CH3 or _C2H5 . ₎

At least one type of unit Y1 selected from the group of the unit represented by the above formula (2) and the unit represented by the above formula (3) will be specifically described below.
When the ester group-containing olefinic copolymer is any one of the following compounds, the melting point of the ester group-containing olefinic copolymer is lower than that of polyethylene, resulting in better low-temperature fixability.
In addition, since the ester group-containing olefinic copolymer acts as an elastomer and tends to exhibit rubber elasticity, it is possible to further suppress burial of the inorganic fine particles.
In addition, polyethylene, which has a high volume resistance, can contain an ester group, which is a polar group, so that the volume resistance can be lowered not a little, and the localization of charges due to triboelectrification can be suppressed. As a result, the electrostatic adhesion force between the intermediate transfer member and the toner can be weakened, resulting in better transferability.
(i) In the unit represented by the formula (2) and the unit represented by the formula (3), ethylene is a copolymer in which ^R1 is H, ^R2 is H, and ^R3 is _CH3 . - vinyl acetate copolymer (ii) in the unit represented by the above formula (2) and the unit represented by the above formula (4), ethylene-acryl wherein R ¹ is H, R ⁴ is H, and R ⁵ is CH ₃ Methyl acid copolymer (iii) A copolymer in which R ¹ is H, R ⁴ is H, and R ⁵ is C ₂ H ₅ in the unit represented by the above formula (2) and the unit represented by the above formula (4) (vi) ethylene-ethyl acrylate copolymer (v) ethylene in which R ¹ is H, R ⁴ is CH ₃ , and R ⁵ is CH ₃ in the units represented by the above formulas (2) and (4) - methyl methacrylate copolymer

In the ester group-containing olefin copolymer, Z1 is the total mass of the ester group-containing olefin copolymer, l is the mass of the units represented by the formulas (2), (3), and (4). When m and n, the value of (l + m + n) / Z1 of the ester group-containing olefin copolymer contained in the resin component is preferably 0.80 to 1.00, preferably 0.95 to It is more preferably 1.00, even more preferably 1.00. When the value of (l+m+n)/Z1 is within the above range, the low-temperature fixability is further improved.

The ester group-containing olefinic copolymer may contain units other than the units Y1 and Y2. Examples of other units include units represented by the following formula (5) and units represented by the following formula (6). These units are introduced by adding corresponding monomers during the copolymerization reaction for producing the ester group-containing olefin copolymer or by modifying the ester group-containing olefin copolymer through a polymer reaction. be able to.

The ester group-containing olefinic copolymer preferably has an ester group concentration of 2.0% by mass to 17.9% by mass with respect to the total mass of the ester group-containing olefinic copolymer. More preferably, it is 11.0% by mass to 15.0% by mass.
The ester group concentration is a value that indicates how much the ester group [-C(=O)O-] bonding site in the ester group-containing olefin copolymer is contained in mass%, and is specifically described below. is a value represented by an expression.
Ester group concentration (unit: %) = [(N x 44) / number average molecular weight] x 100
Here, N is the average number of ester groups per molecule of the ester group-containing olefinic copolymer, and 44 is the formula weight of the ester group [-C(=O)O-]. The number average molecular weight is the number average molecular weight of the ester group-containing olefinic copolymer.

When the ester group concentration is 2.0% by mass to 17.9% by mass with respect to the total mass of the ester group-containing olefin copolymer, the melting point is lower than that of polyethylene within the range that can ensure the storage stability of the toner. Since it can be designed, it is preferable from the viewpoint of low-temperature fixability. In addition, the ester group-containing olefin-based copolymer easily exhibits rubber elasticity as an elastomer, and embedding of inorganic fine particles is further reduced, which is preferable from the viewpoint of transferability. Furthermore, a polymer having a stronger polarity than polyethylene can be used within a range that can ensure the storage stability of the toner, the volume resistance can be further lowered, and the localization of charges due to triboelectrification can be suppressed. As a result, the electrostatic adhesion force between the intermediate transfer member and the toner can be weakened, which is preferable from the viewpoint of transferability.

The acid value of the ester group-containing olefinic copolymer is preferably 10 mgKOH/g or less, more preferably 5 mgKOH/g or less, and still more preferably substantially 0 mgKOH/g. When the acid value of the ester group-containing olefin copolymer is within the above range, the amount of moisture adsorbed by the toner is small, which is preferable from the viewpoint of charge retention.

Further, the toner may be used as long as the resin present on the surface of the toner particles has the rubber elastic properties as described above. The resin existing on the surface of the toner particles and the resin existing inside the toner particles may have the same structure, or may have different structures.
As the resin having a different structure, various resin compounds conventionally known as amorphous resins can be used in addition to the polyester resin described later.
Examples of such amorphous resins include phenol resins, natural resin-modified phenol resins, natural resin-modified maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate resins, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, Epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaroindene resin, petroleum resin, and the like.

When a polyester resin is used as the amorphous resin, for example, a polyester resin having the following structure can be used.
Monomers used in the polyester unit of the polyester resin include polyhydric alcohols (divalent or trivalent or higher alcohols), polyvalent carboxylic acids (divalent or trivalent or higher carboxylic acids), their acid anhydrides or their lower Alkyl esters can be used.
For the polyester resin, for example, the following polyhydric alcohol monomers can be used.
Dihydric alcohol components include, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or bisphenol represented by formula (A) and derivatives thereof; diols represented by formula (B) ; and the like.

（式中、Ｒはエチレンまたはプロピレン基であり、ｘおよびｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０～１０である。）

(Wherein, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 to 10.)

（式中、Ｒ’は

を示し、
ｘ’，ｙ’は０以上の整数であり、且つ、ｘ’＋ｙ’の平均値は０～１０である。）

(In the formula, R' is

indicates
x' and y' are integers of 0 or more, and the average value of x'+y' is 0-10. )

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,4-butanetriol. , 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene mentioned. Among these, glycerol, trimethylolpropane, and pentaerythritol are preferably used. These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination.

The following polyvalent carboxylic acid monomers can be used for the polyester resin.
Examples of divalent carboxylic acid components include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids and Lower alkyl esters of these are included. Among these, maleic acid, fumaric acid, terephthalic acid, succinic acid and n-dodecenylsuccinic acid are preferably used.
Trivalent or higher carboxylic acids, acid anhydrides or lower alkyl esters thereof include, for example, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid. , 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra( methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimer acid, their acid anhydrides or their lower alkyl esters.
Among these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or its derivatives, terephthalic acid and succinic acid are particularly preferred because they are inexpensive and reaction control is easy. These bivalent carboxylic acids and trivalent or higher carboxylic acids can be used alone or in combination.

The method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the alcohol monomer and the carboxylic acid monomer described above can be charged at the same time and polymerized through an esterification reaction or a transesterification reaction and a condensation reaction to produce a polyester resin.
Also, the polymerization temperature is not particularly limited, but is preferably in the range of 180°C to 290°C. Polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used for the polymerization of the polyester units. Of these, tin-based catalysts and titanium-based catalysts are preferred.

Moreover, the polyester resin may be a hybrid resin in which another resin component is contained in the polyester resin. Examples thereof include hybrid resins of polyester resins and vinyl resins. As a method for obtaining a reaction product of a vinyl-based resin or a vinyl-based copolymer unit and a polyester resin, such as a hybrid resin, a monomer component capable of reacting with each of the vinyl-based resin, the vinyl-based copolymer unit and the polyester resin is included. Preferred is the method of conducting the polymerization reaction of either or both resins in the presence of the polymer.
For example, among the monomers constituting the polyester resin component, monomers capable of reacting with the vinyl copolymer include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid, and anhydrides thereof. mentioned.
On the other hand, monomers constituting the vinyl-based resin component that can react with the polyester resin component include, for example, monomers having a carboxy group or a hydroxy group, acrylic acid esters or methacrylic acid esters.

The toner particles may contain a release agent. Release agents include, for example, low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point) upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide; Ester waxes such as stearyl stearate; vegetable waxes such as carnauba wax, rice wax, candelilla wax, Japan wax, and jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline. mineral and petroleum waxes such as waxes, Fischer-Tropsch waxes and ester waxes; or silicone oils.
The content of the release agent is preferably 5 parts by mass to 30 parts by mass with respect to the total amount of the resin components.

Examples of silicone oils that can be used include dimethylsilicone oil, methylphenylsilicone oil, methylhydrogensilicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, alkyl-modified silicone oil, and fluorine-modified silicone oil. Among these, dimethyl silicone oil is preferable from the viewpoint of hot offset resistance.
When the silicone oil is dimethyl silicone oil, the polarity difference with the ester group-containing olefin copolymer is large, so the silicone oil tends to seep out during fixing. As a result, hot offset resistance is further improved.
The content of the silicone oil is preferably 15 parts by mass to 30 parts by mass with respect to the total amount of the resin components. Within this range, the silicone oil oozes out sufficiently during fixing, and the hot offset resistance is further improved.
The kinematic viscosity of silicone oil at 25° C. is preferably 300 mm ² /s to 1000 mm ² /s. Within this range, the silicone oil oozes out sufficiently during fixing, and the hot offset resistance is further improved.

<Colorant>
The toner particles may contain a colorant. Examples of colorants include the following.
Examples of black colorants include those toned black using carbon black; a yellow colorant, a magenta colorant and a cyan colorant. A pigment may be used alone as a coloring agent, but it is more preferable to use a dye and a pigment in combination to improve the definition from the viewpoint of image quality of a full-color image.
Examples of magenta toner pigments include the following. 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, 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, 123, 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 magenta toner dyes include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. disperse thread 9;C. 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; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
Examples of cyan toner pigments 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 1 to 5 phthalimidomethyl groups.
Examples of cyan toner dyes include C.I. I. Solvent Blue 70 can be mentioned.
Examples of yellow toner pigments 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, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat Yellow 1, 3, 20.
Examples of yellow toner dyes include C.I. I. Solvent Yellow 162 is mentioned.
These colorants can be used singly or in combination of two or more, or in the form of a solid solution. Colorants can be selected in terms of hue angle, chroma, brightness, lightfastness, OHP transparency, dispersibility in toner, and the like.
The content of the colorant is preferably 0.1 parts by mass to 30.0 parts by mass with respect to the total amount of the resin components.

<Developer>
The toner can be used as a one-component developer, but in order to further improve dot reproducibility and to supply stable images over a long period of time, it can be mixed with a magnetic carrier and used as a two-component developer. can also be used.
The magnetic carrier includes, for example, iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths, alloy particles thereof, oxide particles thereof; A magnetic material such as ferrite; a magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state; and the like can be used.
When the toner is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carrier at that time is 2% by mass to 15% by mass as the toner concentration in the two-component developer. It is preferably 4% by mass to 13% by mass, more preferably 4% by mass to 13% by mass.

<Toner Manufacturing Method>
The toner particles can be produced by any method, but are preferably toner particles produced in an aqueous medium. The method of producing toner particles in an aqueous medium is preferably used because the resin can be localized on the surface of the toner particles regardless of the mechanical properties of the resin.
Specifically, toner particles can be produced in an aqueous medium by a production method such as a dissolution suspension method or an emulsion aggregation method. In the dissolution suspension method, by controlling the polarity of the resin constituting the toner particles, it is possible to control the resin to spontaneously exist on the surface of the toner particles. In the emulsion aggregation method, the surface of the toner particles can be geometrically controlled by first producing core particles in an aqueous medium and then subjecting them to an aggregation reaction with shell particles, as will be described later. Therefore, from the viewpoint of chargeability (especially chargeability in a high-humidity environment) and from the viewpoint that toner particles can be produced regardless of the polarity of the resin, it is preferable to produce toner particles by an emulsion aggregation method.

<Emulsion aggregation method>
In the emulsion aggregation method, an aqueous dispersion of fine particles containing constituent materials of toner particles, which is sufficiently small with respect to the target particle size, is prepared in advance, and the fine particles are adjusted to the particle size of toner particles in an aqueous medium. In this method, the toner particles are produced by aggregating to a point where the resin is fused by heating.
That is, in the emulsion aggregation method, a dispersing step of preparing a fine particle dispersion liquid containing a constituent material of toner particles, aggregating fine particles containing the constituent material of toner particles, and controlling the particle diameter until it reaches the particle diameter of the toner particles. a fusing step of fusing the resin contained in the obtained agglomerated particles, a subsequent cooling step, a metal removing step of filtering the obtained toner particles to remove excess polyvalent metal ions, and ion exchange. Toner particles can be produced through a filtration/washing step of washing with water or the like, and a step of removing moisture from the washed toner particles and drying them.
In the emulsion aggregation method, if necessary, the wet cake of toner particles obtained in the step of contacting with an organic solvent and the step of separation, the step of treating the wet cake of toner particles obtained in the filtration/washing step, with an organic solvent, or finally the drying step. A step of treating the obtained toner particles with an organic solvent can be carried out.

<Dispersion process>
<Resin Fine Particle Dispersion>
The fine resin particle dispersion can be prepared by a known method, but is not limited to these methods. Known methods include, for example, an emulsion polymerization method, a self-emulsification method, a phase inversion emulsification method in which a resin is emulsified by adding an aqueous medium to a resin solution dissolved in an organic solvent, and a method that does not use an organic solvent. , a forced emulsification method in which a resin is forcibly emulsified by high-temperature treatment in an aqueous medium.
Specifically, the resin is dissolved in an organic solvent in which these are dissolved, and a surfactant and a basic compound are added. At that time, if the resin is a crystalline resin having a melting point, it may be dissolved by heating to a temperature higher than the melting point. Subsequently, while stirring with a homogenizer or the like, the aqueous medium is slowly added to precipitate the fine resin particles. After that, the solvent is removed by heating or reducing the pressure to prepare an aqueous dispersion of fine resin particles.
Here, as the organic solvent used for dissolving the ester group-containing olefinic copolymer, any solvent can be used as long as it can dissolve the ester group-containing olefinic copolymer. From the viewpoint of suppressing the generation of coarse powder, it is preferable to use an organic solvent that forms a homogeneous phase with water.
The surfactant used in the dispersing step is not particularly limited, and examples thereof include anionic surfactants such as sulfate-based, sulfonate-based, carboxylate-based, phosphate-based, and soap-based surfactants. cationic surfactants such as amine salt type and quaternary ammonium salt type; nonionic surfactants such as polyethylene glycol type, alkylphenol ethylene oxide adduct type and polyhydric alcohol type; Surfactants may be used singly or in combination of two or more.
Basic compounds used in the dispersing step include, for example, inorganic bases such as sodium hydroxide and potassium hydroxide; organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol and diethylaminoethanol. A basic compound may be used individually by 1 type, and may use 2 or more types together.
Further, the dispersed particle size of the fine resin particles in the aqueous dispersion is 50% particle size based on volume distribution, from the viewpoint that it is easy to obtain toner particles having a volume average particle size of 3 μm to 10 μm, which is suitable as toner particles. (D50) is preferably 0.05 μm to 1.0 μm, more preferably 0.05 μm to 0.4 μm. A dynamic light scattering particle size distribution analyzer, Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), can be used to measure the 50% particle size (D50) based on volume distribution.

<Colorant Fine Particle Dispersion>
The colorant fine particle dispersion liquid used as necessary can be prepared by the following known methods, but is not limited to these methods.
The colorant fine particle dispersion can be prepared by mixing components such as a colorant, an aqueous medium and a dispersant using a known mixer such as a stirrer, an emulsifier and a disperser. As the dispersant used here, known dispersants such as surfactants and polymer dispersants can be used.
Both surfactants and polymeric dispersants can be removed in the cleaning step described below, but surfactants are preferred from the viewpoint of cleaning efficiency.
Examples of surfactants include anionic surfactants such as sulfate-based, sulfonate-based, phosphate-based, and soap-based surfactants; cationic surfactants such as amine salt-type and quaternary ammonium salt-type; polyethylene Examples include nonionic surfactants such as glycol-based surfactants, alkylphenol ethylene oxide adduct-based surfactants, and polyhydric alcohol-based surfactants.
Among these, nonionic surfactants or anionic surfactants are preferred. Moreover, you may use a nonionic surfactant and an anionic surfactant together. Surfactants may be used singly or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably 0.5% by mass to 5% by mass.
The content of the fine coloring agent particles in the fine coloring agent dispersion is not particularly limited, but is preferably 1% by mass to 30% by mass relative to the total mass of the fine coloring agent dispersion.
Further, from the viewpoint of the dispersibility of the colorant in the finally obtained toner, the dispersed particle size of the fine colorant particles in the aqueous dispersion is 0.5 μm or less based on volume distribution (D50). is preferably For the same reason, the 90% particle diameter (D90) based on volume distribution is preferably 2 μm or less.
The dispersed particle size of the colorant fine particles dispersed in the aqueous medium is measured with a dynamic light scattering particle size distribution meter (Nanotrac UPA-EX150, manufactured by Nikkiso).
Known mixers such as stirrers, emulsifiers, and dispersers used for dispersing the colorant in an aqueous medium include, for example, ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, and sand mills. , and paint shakers. These may be used alone or in combination.

<Releasing agent fine particle dispersion>
The aqueous dispersion of release agent fine particles used as necessary has, for example, a release agent added to an aqueous medium containing a surfactant, heated to the melting point of the release agent or higher, and has a strong shear imparting ability. After dispersing into particles with a homogenizer (e.g., M Technic's "Clearmix W Motion") or a pressure discharge type disperser (e.g., Gorlin's "Golin Homogenizer"), cooling to below the melting point. can be made with
Regarding the dispersed particle size of the release agent fine particles in the aqueous dispersion, the volume-based 50% particle size (d50) is preferably 0.03 μm to 1.0 μm, more preferably 0.1 μm to 0.5 μm. more preferred. Further, it is more preferable that coarse particles with d50 exceeding 1.0 μm do not exist.
When the dispersed particle size of the release agent fine particles is within the above range, the release agent can be eluted better during fixing, the hot offset temperature can be increased, and filming on the photoreceptor can occur. can be suppressed. The dispersed particle size of the release agent fine particles dispersed in the aqueous medium can be measured by a dynamic light scattering type particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) or the like.

When silicone oil is used as the release agent, it is preferable to prepare a composite fine particle dispersion by mixing a resin constituting toner particles and silicone oil. By doing so, the amount of silicone oil on the surfaces of the toner particles can be easily adjusted to an appropriate range while increasing the silicone oil content in the toner particles, so that the transfer efficiency is improved.
Specifically, silicone oil may be mixed with a solution obtained by dissolving a resin in an organic solvent in the step of preparing the fine resin particle dispersion.
In addition, the silicone oil fine particle dispersion can be separately prepared by the following known methods, but is not limited to these methods.
It can be prepared by mixing silicone oil, aqueous medium and dispersant by known mixers such as stirrers, emulsifiers and dispersers. As the dispersant used here, known dispersants such as surfactants and polymer dispersants can be used.
Both surfactants and polymeric dispersants can be removed in the cleaning step described below, but surfactants are preferred from the viewpoint of cleaning efficiency.
Examples of surfactants include anionic surfactants such as sulfate-based, sulfonate-based, phosphate-based, and soap-based surfactants; cationic surfactants such as amine salt-type and quaternary ammonium salt-type surfactants; Examples include nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adducts, and polyhydric alcohol-based surfactants.
Among these, nonionic surfactants or anionic surfactants are preferred. Moreover, you may use a nonionic surfactant and an anionic surfactant together. Surfactants may be used singly or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably 0.5% by mass to 5% by mass.

Although the content of the silicone oil fine particles in the silicone oil fine particle dispersion is not particularly limited, it is preferably 1% by mass to 30% by mass relative to the total mass of the silicone oil fine particle dispersion.
Further, from the viewpoint of easy control of the amount of silicone oil on the surface of the toner, the dispersed particle size of the silicone oil in the aqueous dispersion preferably has a volume-based 50% particle size (D50) of 0.5 μm or less. For the same reason, it is preferable that the volume-based 90% particle diameter (D90) is 2.0 μm or less.
The dispersed particle size of the silicone compound dispersed in the aqueous medium can be measured by dynamic light scattering particle size distribution (Nanotrack, manufactured by Nikkiso).
Known mixers such as stirrers, emulsifiers, and dispersers used for dispersing silicone oil in an aqueous medium include, for example, ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, sand mills, and paint shakers. These may be used alone or in combination.

<Mixing process>
In the mixing step, a mixed liquid can be prepared by mixing a fine resin particle dispersion and, if necessary, a release agent fine particle dispersion, a colorant fine particle dispersion, and the like. Mixing can be performed, for example, using a known mixing device such as a homogenizer and a mixer.

<Aggregation process>
In the aggregation step, the fine particles contained in the mixed liquid prepared in the mixing step can be aggregated to form an aggregate having a desired particle size. At this time, an aggregating agent is added and mixed, and if necessary, at least one of heating and mechanical power is appropriately applied to obtain resin fine particles, and
If necessary, aggregates can be formed by aggregating release agent fine particles, colorant fine particles, and the like. When the core-shell structure is formed in the toner particles, it is preferable to mix and coagulate particles other than the fine particle dispersion liquid of the resin forming the shell, and then add the fine particle dispersion liquid of the resin forming the shell and coagulate.
As the flocculant, it is preferable to use a flocculant containing a metal ion having a valence of 2 or more. A flocculant containing at least one metal ion selected from the group consisting of Mg, Ca, Sr, Al, and Zn is more preferred.
A flocculant containing a metal ion with a valence of 2 or higher has a high cohesive force and can achieve the purpose by adding a small amount. These flocculants can ionically neutralize the ionic surfactants contained in the fine resin particle dispersion, release agent dispersion, and colorant fine particle dispersion. As a result, the effects of salting out and ionic cross-linking make it possible to agglomerate the fine resin particles, the fine particles of the release agent, and the fine particles of the colorant.

Examples of the flocculant containing a divalent or higher valent metal ion include a divalent or higher valent metal salt or a polymer of a metal salt. Specific examples include divalent inorganic metal salts such as calcium chloride, calcium nitrate, magnesium chloride, magnesium sulfate, and zinc chloride. Also included are trivalent metal salts such as iron(III) chloride, iron(III) sulfate, aluminum sulfate, and aluminum chloride. Further, non-limiting examples include inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. These may be used individually by 1 type, and may use 2 or more types together.
The flocculant may be added in the form of either a dry powder or an aqueous solution dissolved in an aqueous medium, but is preferably added in the form of an aqueous solution in order to cause uniform aggregation.
Addition and mixing of the flocculant are preferably carried out at a temperature equal to or lower than the glass transition temperature or melting point of the resin contained in the mixture. Aggregation can proceed relatively uniformly by performing mixing under this temperature condition. Mixing of the flocculant into the liquid mixture can be performed using a known mixing device such as a homogenizer and a mixer.
The aggregating step is a step of forming aggregates having a particle size similar to that of toner particles in an aqueous medium. The volume-based 50% particle diameter (D50) of the aggregates produced in the aggregation step is preferably 3 μm to 10 μm.

<Fusion process>
In the fusion step, an aggregation terminator can be added to the dispersion containing the aggregates obtained in the aggregation step under the same stirring as in the aggregation step. The aggregation terminator includes a basic compound that stabilizes aggregated particles by shifting the equilibrium of the acidic polar group of the surfactant to the dissociation side. In addition, a chelating agent that stabilizes aggregated particles by partially dissociating the ionic bridge between the acidic polar group of the surfactant and the metal ion contained in the flocculant and forming a coordinate bond with the metal ion, etc. mentioned. Among these, a chelating agent having a greater effect of stopping aggregation is preferred.
After the dispersed state of the aggregated particles in the dispersion liquid is stabilized by the action of the aggregation terminator, the aggregated particles can be fused by heating above the glass transition temperature or melting point of the binder resin.

The chelating agent is not particularly limited as long as it is a known water-soluble chelating agent. Specifically, oxycarboxylic acids such as, for example, tartaric acid, citric acid, and gluconic acid, and their sodium salts; iminodiacid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA), and These sodium salts;
The chelating agent coordinates with the metal ions of the flocculant present in the dispersion liquid of the aggregated particles, thereby changing the environment in the dispersion liquid from an electrostatically unstable state that tends to aggregate to an electrostatic state. It can be changed to a stable state in which further aggregation is unlikely to occur. As a result, further aggregation of the aggregated particles in the dispersion can be suppressed, and the aggregated particles can be stabilized.
The chelating agent is preferably an organometallic salt having a carboxylic acid having a valence of 3 or more, because it is effective even when added in a small amount, and toner particles having a sharp particle size distribution can be obtained.
The amount of the chelating agent to be added is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of achieving both stabilization from the aggregation state and cleaning efficiency, and 2.5 parts by mass. It is more preferably 15 parts by mass to 15 parts by mass. The volume-based 50% particle size (D50) of the toner particles is preferably 3 μm to 10 μm.

<Cooling process>
The cooling step is a step of cooling the temperature of the dispersion containing the toner particles obtained in the coalescing step to a temperature lower than at least one of the crystallization temperature and the glass transition temperature of the binder resin. Unless the cooling is performed to a temperature lower than at least one of the crystallization temperature and the glass transition temperature, coarse particles are generated. A specific cooling rate can be 0.1° C./min to 50° C./min.

<Metal removal step>
The method for producing a toner may include a metal removing step of adding a chelate compound having a chelating ability to metal ions to remove the metal ions. The chelating compound is not particularly limited as long as it is a known water-soluble chelating agent, and the above chelating agents can be used.

<Washing process>
In the washing step, impurities in the toner particles can be removed by repeating washing and filtering of the toner particles obtained in the cooling step. Specifically, it is preferable to wash the toner particles with an aqueous solution containing a chelating agent such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, and then wash with pure water. By repeating washing with pure water and filtering multiple times, metal salts, surfactants, and the like in the toner particles can be removed more efficiently. The number of times of filtration is preferably 3 to 20 times, more preferably 3 to 10 times, from the viewpoint of production efficiency.

<Step of contacting with organic solvent and separation step>
In the step of contacting with an organic solvent and the step of separating, if necessary, the toner particles obtained in the washing step can be brought into contact with an organic solvent and separated. By this step, the low-molecular-weight silicone compound that has a high affinity for the organic solvent is washed off, and a thin film of the silicone compound with a sharp molecular weight distribution can be formed on the surface of the toner particles.
It is preferable that the organic solvent used in this step is lower than a certain level of affinity with the silicone compound, unlike a conventional solvent that cleans the mold release agent. If the affinity is too high, the silicone compound, which is the releasing agent, will be pulled out too much from the toner particles, resulting in a decrease in fixing separability. Therefore, it is preferable to control the affinity between the organic solvent and the silicone compound. Specific organic solvents include, for example, ethanol, methanol, propanol, isopropanol, ethyl acetate, methyl acetate, butyl acetate, and mixtures thereof.

The organic solvent may contain water, and the water content is preferably 0 to 10 parts by mass with respect to 100 parts by mass of the organic solvent. Within the above range, the low-molecular-weight silicone compound in the vicinity of the surface of the toner particles is easily removed.
The treatment time for the step of contacting the toner particles with the organic solvent is preferably from 1 minute to 60 minutes.
In the step of contacting the toner particles and the organic solvent, when the toner particles and the organic solvent are mixed to obtain an organic solvent dispersion of the toner particles, the stirring may be performed by stirring with a stirring blade, or may be performed by stirring with a homogenizer, an ultrasonic disperser, or the like. However, from the viewpoint of uniformly treating the toner particles, it is preferable to perform the treatment while stirring with a homogenizer, an ultrasonic disperser, or the like.
The step of separating the toner particles and the organic solvent is a step of physically separating the organic solvent dispersion of the toner particles obtained in the contact step or the mixture of the toner wet cake and the organic solvent by filtration or the like. The separation method is not particularly limited as long as the toner particles and the organic solvent can be separated, and examples thereof include suction filtration, pressure filtration, and centrifugation.
The step of contacting and separating the toner particles and the organic solvent may be carried out by repeating the contacting and separating steps a plurality of times. In particular, when treating a mixture of the toner wet cake and the organic solvent, the removal efficiency of the silicone compound may be lowered due to the influence of water present in the toner wet cake, so it is preferable to perform the treatment multiple times.

<Drying process>
In the drying process, the toner particles obtained in the above process are dried.

<External Addition Process>
In the external addition step, inorganic fine particles having a rectangular parallelepiped particle shape are externally added to the toner particles. In the external addition step, a known external additive other than the inorganic fine particles having a rectangular parallelepiped particle shape may be externally added.
Specifically, inorganic fine particles such as silica, alumina, titania, and calcium carbonate, resin fine particles such as vinyl resins, polyester resins, and silicone resins, and inorganic fine particles having a rectangular parallelepiped particle shape are dried. It is preferably added by applying a shear force.

Methods for measuring various physical properties of toner and raw materials are described below.

<Method for measuring displacement h and plastic deformation rate H>
The displacement h and the plastic deformation rate H of the resin present on the toner surface are measured using an ultra-micro indentation hardness tester "ENT1100a" (manufactured by Elionix), which is one of ultra-micro hardness measuring devices.
The resin present on the surface of the toner particles is spread on the stage, and while checking with an optical microscope, the stage is moved so that one particle of resin present on the surface of the toner particles is in the center, the position information is recorded, and the measurement is performed. I do.
Measurement conditions are as follows.
Load: 50 μN
Temperature: 25°C
Number of divisions: 1000 times Step interval: 50msec
Indenter: 50 μm flat indenter The measurement results of the resin used in Example 1 are shown in FIG. Displacement h is the displacement when a test load of 50 μN is applied. The plastic deformation rate H is calculated using the following formula by reading the displacement x that has not completely returned when the test load is returned to 0 μN after applying a test load of 50 μN.
Plastic deformation rate H = {displacement x/displacement h} x 100
When measuring from the toner, the displacement h and the plastic deformation rate H are determined using the resin after the resin present on the surface of the toner particles is separated from the toner by the method described later.

<Method for measuring SP values (SP1 and SP2)>
The SP values (SP1 and SP2, respectively) of the resin present on the surface of the toner particles and the surface treatment agent of the inorganic fine particles are obtained by identifying the chemical structure by NMR, calculating the molar ratio, and then using the Fedors equation. Use Here, the values of Δei and Δvi are the vaporization energies and molar volumes ( 25°C).
Formula: δi=[Ev/V] ^1/2 =[Δei/Δvi] ^1/2
Ev: Evaporation energy V: Molar volume Δei: Evaporation energy of the atom or atomic group of component i Δvi: Molar volume of the atom or atomic group of component i The monomer structure and molar ratio of the ester group-containing olefin-based copolymer are ¹ H Determined by NMR. Under the following conditions, the integral ratio of hydrogen in the side chain of the monomer structure of the ester group-containing olefin copolymer is measured and compared to calculate the unit ratio.
Apparatus: JNM-ECZR series FT NMR (manufactured by JEOL JEOL Ltd.)
Solvent: 5 mL deuterated acetone (tetramethylsilane included as an internal standard with a chemical shift of 0.00 ppm)
Sample: 5mg
Repeat time: 2.7 seconds Accumulation times: 16 times For example, the unit ratio of the ester group-containing olefin copolymer 1 (ethylene-vinyl acetate copolymer) used in Example 1 was calculated to Since the peak at 0.36 ppm corresponds to CH ₂ —CH ₂ of the ethylene unit and the peak near 2.04 ppm corresponds to CH ₃ of the vinyl acetate unit, the ratio of the integrated values of these peaks is calculated.
From the obtained molar ratio, the SP value is calculated using the Fedors formula.

<Method for measuring surface potential B>
The surface potential B is derived by carrying out the following rubbing test using the inorganic fine particles and the resin existing on the surface of the toner particles.
First, a resin piece is produced using a resin existing on the surface of a toner particle. Resin pieces are made by applying pressure on a hot plate heated above the melting point of the resin.
Next, static electricity is removed from the surface of the produced resin piece by a static eliminator. An X-ray generator (Photoionizer manufactured by Hamamatsu Photonics Co., Ltd.) is used to irradiate the resin piece with X-rays (tube voltage: 15 kV, irradiation angle: 130°) for 30 seconds or more to remove static electricity from the resin piece. It is confirmed that the potential of the resin piece is -50 V to +50 V with a surface potential meter (model 347 manufactured by Trek Japan) to confirm that no potential remains on the resin piece. Here, the distance between the surface potential meter and the resin piece is 1 cm.
Next, the inorganic fine particles are placed on the resin piece, and the inorganic fine particles are sandwiched between another resin piece prepared in the same manner, and rubbed back and forth 30 times.
Here, surface potential D is the surface potential of the resin piece measured with the inorganic fine particles adhering to the resin piece.
A surface potential E is defined as a surface potential E measured using a piece of resin from which the inorganic fine particles have been removed by air blowing so as not to generate triboelectrification.
By calculating the difference between these surface potentials D and E, the surface potential B is calculated.

That is, the surface potential B can be obtained by the following formula.
Surface potential B=(Surface potential D of the resin pieces measured in a state where the inorganic fine particles adhere to the resin pieces after rubbing the resin pieces of the resin present on the surface of the toner particles with the inorganic fine particles)- (Surface potential E measured using a resin piece obtained by removing the inorganic fine particles by air blow after rubbing the resin pieces of the resin present on the surface of the toner particles with the inorganic fine particles)
When measuring from the toner, the surface potential B can be obtained using the resin and inorganic fine particles after separating the resin and inorganic fine particles present on the surface of the toner particles from the toner by the method described later.

<Method for measuring shape and number average particle diameter (D1) of primary particles of inorganic fine particles>
The number average particle diameter of the primary particles of the inorganic fine particles is obtained by observing the inorganic fine particles present on the toner particle surface with a scanning electron microscope. As a scanning electron microscope, a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (manufactured by Hitachi, Ltd.) is used. The imaging conditions for the S-4800 are as follows. Elemental analysis is performed in advance using an energy dispersive X-ray spectrometer (manufactured by EDAX) to confirm that each particle is silica fine particles or titanium oxide fine particles before measurement.

(1) Sample Preparation A sample stage (aluminum sample stage 15 mm×6 mm) is thinly coated with conductive paste, and toner is sprayed thereon. Further, air blowing is performed to remove excess toner from the sample stage, and the sample stage is sufficiently dried. A sample stage is set on the sample holder, and the height of the sample stage is adjusted to 36 mm using the sample height gauge.
(2) S-4800 Observation Condition Setting The number average particle diameter of the primary particles of the inorganic fine particles is calculated using an image obtained by S-4800 backscattered electron image observation. Since the backscattered electron image has less charge-up of the inorganic fine particles than the secondary electron image, the particle size of the inorganic fine particles can be measured with high accuracy.
The anti-contamination trap attached to the S-4800 housing is flooded with liquid nitrogen and left for 30 minutes. Start "PCSTEM" of S-4800 and perform flushing (cleaning of the FE chip which is the electron source). Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2 and execute. Confirm that the emission current due to flashing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position. Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [0.8 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Upper (U)] and [+BSE] for the SE detector, and select [ L. A. 100] to set the mode for observing backscattered electron images. Similarly, in the [Basic] tab of the operation panel, set the probe current in the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [3.0 mm]. Press the [ON] button on the acceleration voltage display section of the control panel to apply the acceleration voltage.
(3) Calculation of Number Average Particle Diameter (D1) of Inorganic Fine Particles Drag within the magnification display section of the control panel to set the magnification to 100000 (100k) times. Rotate the focus knob [COARSE] on the operation panel, and adjust the aperture alignment when the focus is achieved to some extent. Click [Align] in the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA/ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circle. Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. This operation is repeated two more times, and the particle size is measured by focusing. The number average particle diameter (D1) is obtained by measuring the particle diameters of at least 300 inorganic fine particles on the surface of the toner particles.

<Method for Measuring Content of Ester Group-Containing Olefin-Based Copolymer>
The content of the ester group-containing olefinic copolymer present on the surface of the toner particles is determined by utilizing the difference in ease of dyeing the amorphous resin and the ester group-containing olefinic copolymer with respect to ruthenium tetroxide. It is calculated by cross-sectional observation of particles.
First, as a specific method for measuring the shape of the cross section of the toner particles, the toner particles are sufficiently dispersed in a photocurable epoxy resin, and then the epoxy resin is cured by irradiating ultraviolet rays. The obtained cured product is cut using a microtome equipped with diamond teeth to prepare flaky samples.
After dyeing the sample with ruthenium tetroxide, the tomographic morphology of the toner particles is observed using a transmission electron microscope (TEM) (H7500, manufactured by HITACHI) at an acceleration voltage of 120 kV. In the observation method described above, the amorphous portion of the toner particles is strongly stained with ruthenium tetroxide. As a result, the portion containing the amorphous resin as the main component is dyed, and the portion containing the ester group-containing olefin copolymer as the main component is not dyed and can be observed as a contrast. Note that the observation magnification is 20000 times. The surface of a toner particle refers to a region of 0 nm to 100 nm from the outer surface of the toner particle toward the center (middle point of the long axis) in cross-sectional observation of the toner using a TEM. The content is calculated from the area ratio of the dyed portion and the non-dyed portion within the above range and the specific gravity of the amorphous resin and the ester group-containing olefin copolymer.

<Method for Measuring Ester Group Concentration of Ester Group-Containing Olefin-Based Copolymer>
The ester group concentration of the ester group-containing olefinic copolymer is determined by ¹ H NMR. Under the following conditions, the integral ratio of hydrogen in the side chain of the monomer structure of the ester group-containing olefin copolymer is measured and compared to calculate the unit ratio. By introducing the obtained unit ratio into the following formula, the ester group concentration is calculated.
Ester group concentration (unit: mass %) = [(N × 44) / number average molecular weight] × 100
Here, N is the average number of ester groups per molecule of the ester group-containing olefinic copolymer, and 44 is the formula weight of the ester group [-C(=O)O-].
Apparatus: JNM-ECZR series FT NMR (manufactured by JEOL JEOL Ltd.)
Solvent: 5 mL deuterated acetone (tetramethylsilane included as an internal standard with a chemical shift of 0.00 ppm)
Sample: 5mg
Repeat time: 2.7 seconds Accumulation times: 16 times For example, the unit ratio of the ester group-containing olefin copolymer 1 (ethylene-vinyl acetate copolymer) used in Example 1 was calculated to Since the peak at 0.36 ppm corresponds to CH ₂ —CH ₂ of the ethylene unit and the peak near 2.04 ppm corresponds to CH ₃ of the vinyl acetate unit, the ratio of the integrated values of these peaks is calculated.

(when measured from toner)
The resin present on the surface of the toner particles and the inorganic fine particles having a rectangular parallelepiped particle shape are separated from the toner by utilizing the difference in solubility in the solvent, and then the above measurement is performed.
In the cross-sectional observation of the toner particles, the resin present on the surface of the toner particles and the rectangular parallelepiped particle shape from the toner in which the resin present on the surface of the toner particles and the resin present inside the toner particles are not the same. Separation of the inorganic fine particles having is performed by the following procedure.
First separation: Toner is dissolved in MEK at 23° C. to separate soluble matter (amorphous resin) and insoluble matter (resin, release agent, colorant, inorganic fine particles present on the surface of toner particles).
Second separation: Intoluene at 50° C., the insoluble matter obtained in the first separation (resin, release agent, colorant, inorganic fine particles present on the surface of the toner particles) is dissolved, and the soluble matter (of the toner particles resin existing on the surface) and insoluble matter (release agent, colorant, inorganic fine particles) are separated.
The above measurement is performed using the obtained insoluble matter (resin present on the surface of the toner particles).

Separation of the resin and the inorganic fine particles having a rectangular parallelepiped particle shape from the toner in which the resin existing on the surface of the toner particles and the resin existing inside the toner particles are the same in the observation of the cross section of the toner particles. is performed in the following steps.
Toner is dissolved in MEK at 23° C. to separate soluble matter (resin) and insoluble matter (releasing agent, colorant, inorganic fine particles).
The above measurements are performed using the obtained soluble matter (resin).

<Method for Measuring Weight Average Particle Size (D4) of Toner>
The weight-average particle diameter (D4) of the toner was measured by a precision particle size distribution measuring device "Coulter Counter Multisizer" by the pore electrical resistance method equipped with a 100 μm aperture tube.
3" (registered trademark, manufactured by Beckman Coulter, Inc.) and the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data, Measure with 25,000 effective measurement channels, analyze the measurement data, and calculate.
The electrolytic aqueous solution used for the measurement can be prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter, Inc.).
Before performing measurement and analysis, set the dedicated software as follows.
In the "change standard measurement method (SOM) screen" of the dedicated software, set the total count number in control mode to 50000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter Co., Ltd. (manufactured) to set the value obtained using By pressing the threshold/noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of aperture tube after measurement.
In the "pulse-to-particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

A specific measuring method is as follows.
(1) About 200 mL of the electrolytic aqueous solution is placed in a 250 mL glass round-bottomed beaker exclusively for Multisizer 3, set on a sample stand, and stirred counterclockwise at 24 rpm with a stirrer rod. Then, remove the dirt and air bubbles inside the aperture tube using the dedicated software's "Flush Aperture Tube" function.
(2) About 30 mL of the electrolytic aqueous solution is placed in a 100 mL flat-bottom glass beaker, and "Contaminon N" (a nonionic surfactant, an anionic surfactant, and an organic builder consisting of an organic builder) is used as a dispersant. About 0.3 mL of a diluent obtained by diluting a 10% by mass aqueous solution of a neutral detergent for washing ware (manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water three times by mass is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with a phase shift of 180 degrees, and an ultrasonic disperser with an electrical output of 120 W "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) in a water tank. A predetermined amount of ion-exchanged water is put into the water tank, and about 2 mL of the contaminon N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker in (4) above is being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank is appropriately adjusted to 10°C to 40°C.
(6) The electrolytic aqueous solution of (5) above, in which the toner is dispersed, is dropped into the round-bottomed beaker of (1) above set in the sample stand, and adjusted so that the measured concentration is about 5%. . Then, the measurement is continued until the number of measured particles reaches 50,000.
(7) Analyze the measurement data with the dedicated software attached to the apparatus, and calculate the weight average particle diameter (D4). The weight average particle size (D4) is the "average diameter" on the "analysis/volume statistics (arithmetic mean)" screen when graph/vol% is set using dedicated software.

<Method for Measuring Average Circularity of Toner>
The average circularity of the toner is measured by a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under measurement and analysis conditions during calibration work.
The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture a still image of flowing particles and perform image analysis. A sample added to the sample chamber is delivered to the flat sheath flow cell by a sample aspiration syringe. The sample fed into the flat sheath flow is sandwiched between the sheath fluids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at intervals of 1/60 second, and it is possible to photograph the flowing particles as a still image. In addition, since the flow is flat, it is imaged in a focused state.
A particle image is captured by a CCD camera, and the captured image is image-processed at an image processing resolution of 512×512 pixels (0.37×0.37 μm per pixel). , the projected area S, the perimeter L, and the like are measured.
Next, using the area S and the perimeter L, the equivalent circle diameter and circularity are determined. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the degree of circularity C is the value obtained by dividing the perimeter of the circle obtained from the equivalent circle diameter by the perimeter of the projected particle image. and is calculated by the following formula.
Circularity C=2×(π×S) ^1/2 /L
When the particle image is circular, the degree of circularity is 1.000. After calculating the circularity of each particle, the range of circularity from 0.200 to 1.000 is divided into 800, the arithmetic mean value of the obtained circularities is calculated, and the value is defined as the average circularity.

A specific measuring method is as follows.
First, about 20 mL of ion-exchanged water, from which solid impurities have been removed in advance, is placed in a glass container. As a dispersant, "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for cleaning precision measuring instruments at pH 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersant. ) is diluted with ion-exchanged water to about 3 times the mass, and about 0.2 mL of the diluted solution is added.
Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion liquid for measurement. At that time, the temperature of the dispersion liquid is appropriately cooled to 10.degree. C. to 40.degree. As the ultrasonic disperser, a tabletop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervoclea)) with an oscillation frequency of 50 kHz and an electrical output of 150 W was used. Replaced water is put in, and about 2 mL of the contaminon N is added to this water bath.
For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10x) is used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion liquid prepared according to the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are counted in the HPF measurement mode and the total count mode.
Then, the average circularity of the toner is determined by setting the binarization threshold during particle analysis to 85% and setting the analyzed particle diameter to a circle equivalent diameter of 1.98 μm to 39.96 μm.
In the measurement, automatic focus adjustment is performed using standard latex particles (for example, "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific diluted with deionized water) before starting the measurement. Preferably, thereafter, focus adjustment is performed every two hours from the start of measurement.

<Method for Measuring 50% Particle Size (D50) Based on Volume Distribution of Fine Resin Particles, Release Agent Fine Particles, and Colorant Fine Particles>
A dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) is used to measure the 50% particle size (D50) based on volume distribution of fine resin particles, release agent fine particles, and colorant fine particles. In order to prevent aggregation of the measurement sample (resin fine particles), a dispersion in which the measurement sample is dispersed is put into an aqueous solution containing Family Fresh (manufactured by Kao Corporation) and stirred. After that, it is injected into the above-mentioned device, measured twice, and the average value is obtained.
As the measurement conditions, the measurement time is 30 seconds, the sample particle refractive index is 1.49, the dispersion medium is water, and the dispersion medium refractive index is 1.33. The volume particle size distribution of the measurement sample is measured, and from the measurement results, the particle size at which the cumulative volume from the small particle size side in the cumulative volume distribution becomes 50% is calculated as the 50% particle size (D50) based on the volume distribution of each fine particle. .

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. All "parts" of each material in Examples and Comparative Examples are based on mass unless otherwise specified.

<Production Example of Ester Group-Containing Olefin-Based Copolymer 1 (R ¹ =H, R ² =H, R ³ =CH ₃ )>
・ 75.2 parts of ethylene (90.3 mol% with respect to the total number of moles)
- Vinyl acetate 24.8 parts (9.7 mol% relative to the total number of moles)
・Isobutyraldehyde (chain transfer agent) 4.2 parts ・Di-t-butyl peroxide (radical generation catalyst) 0.0025 parts Weigh the above materials and use a high-pressure pump to pump them into a tubular reactor, and the reaction pressure Ethylene and vinyl acetate were copolymerized under polymerization conditions of 240 MPa and a reaction peak temperature of 250° C. to obtain an ester group-containing olefinic copolymer 1 . The resulting ester group-containing olefin copolymer 1 has a weight average molecular weight (Mw) of 110,000, a melting point (Tp) of 86°C, a melt flow rate (MFR) of 12 g/10 minutes, and an acid value (Av) of 0 mgKOH. /g.

<Production Examples of Ester Group-Containing Olefin-Based Copolymers 2 to 6>
In the production example of the ester group-containing olefin copolymer 1, the reaction was carried out in the same manner except that the respective monomers and parts by mass were changed as shown in Table 1, to obtain ester group-containing olefin copolymers 2 to 6. Obtained.

<Production Example of Amorphous Resin 1>
・Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane
76.3 parts (50.0 mol% relative to the total number of moles)
・ 16.1 parts of terephthalic acid (30.0 mol% relative to the total number of moles)
・ 7.6 parts of succinic acid (20.0 mol% relative to the total number of moles)
- Titanium tetrabutoxide (esterification catalyst) 0.5 part The above materials were weighed into a reactor equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple.
Next, after the inside of the reaction vessel was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200°C.
tert-butyl catechol (polymerization inhibitor) 0.1 part Then, after confirming that the softening point measured according to ASTM D36-86 has reached the desired temperature, add the above materials and lower the temperature to stop the reaction. , an amorphous resin 1 was obtained.
The obtained amorphous resin 1 had a weight average molecular weight (Mw) of 9000, a softening point (Tm) of 100°C, a glass transition temperature (Tg) of 60°C, and an acid value (Av) of 5 mgKOH/g. .

<Production example of inorganic fine particles 1>
Metatitanic acid obtained by the sulfuric acid method was deironized and bleached, then adjusted to pH 9.0 with an aqueous sodium hydroxide solution, desulfurized, neutralized to pH 5.8 with hydrochloric acid, filtered and washed with water. Water was added to the washed cake to obtain a slurry of 1.5 mol/L as TiO ₂ , and then hydrochloric acid was added to adjust the pH to 1.5 for deflocculation.
The desulfurized and deflocculated metatitanic acid was collected as TiO ₂ and put into a 3 L reactor. After adding an aqueous solution of strontium chloride to the peptized metatitanic acid slurry so that the SrO/TiO ₂ molar ratio was 1.15, the TiO ₂ concentration was adjusted to 0.8 mol/L. Next, after heating to 90 ° C. while stirring and mixing, 444 mL of a 10 mol / L sodium hydroxide aqueous solution was added over 50 minutes while performing nitrogen gas micro-bubbling at 600 ml / min, and then nitrogen gas micro-bubbling. was stirred at 95° C. for 1 hour while performing at 200 ml/min.
After that, the reaction slurry was stirred while cooling water at 10°C was flown through the jacket of the reaction vessel, and was rapidly cooled to 15°C at a cooling rate of 10°C/min. rice field. After washing the obtained precipitate by decantation, 6 mol/L hydrochloric acid was added to adjust the pH to 2.0, 8.0% by mass of n-octylethoxysilane was added to the solid content, and the mixture was stirred for 18 hours. rice field. After neutralization with a 4 mol/L sodium hydroxide aqueous solution and stirring for 2 hours, filtration/separation was carried out, followed by drying in the air at 120° C. for 8 hours to obtain inorganic fine particles 1 . When the shape was observed by electron microscope observation, it was found to be cubic, and the average primary particle size calculated on a number basis was 50 nm. Physical properties are shown in Table 2.

<Production Examples of Inorganic Fine Particles 2 to 10>
Inorganic fine particles 2 to 9 were produced in the same manner as inorganic fine particles 1 by changing the type of base material, the addition time of the 10 mol/L sodium hydroxide aqueous solution, the cooling rate, and the type of surface treatment agent. Physical properties are shown in Table 2.

シリコーンオイル：ジメチルシリコーンオイル（信越化学製ＫＦ９６－５００ＣＳ）

Silicone oil: dimethyl silicone oil (KF96-500CS manufactured by Shin-Etsu Chemical)

<Production Example of Ester Group-Containing Olefin Copolymer Fine Particle 1 Dispersion>
- Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts - Ester group-containing olefin copolymer 1 100 parts The above materials were weighed, mixed, and dissolved at 90°C.
Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700 parts of ion-exchanged water and dissolved by heating at 90°C. Next, the above toluene solution and the aqueous solution are mixed, and the ultra-high speed stirrer T.I. K. The mixture was stirred at 7000 r/min using Robomix (manufactured by Primix). Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, the toluene is removed using an evaporator, and the concentration is adjusted with ion-exchanged water. liquid) was obtained.
When the 50% particle size (D50) based on volume distribution of the ester group-containing olefin copolymer fine particles 1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0. It was 40 μm. Physical properties are shown in Table 3.

<Production Example of Ester Group-Containing Olefin Copolymer Fine Particles 2 to 5 Dispersion>
Emulsification was carried out in the same manner as in Production Example of Ester Group-Containing Olefin Copolymer Fine Particles 1 Dispersion, except that the respective ester group-containing olefin copolymers were changed as shown in Table 3. Copolymer fine particle 2-5 dispersions were obtained. Table 3 shows the physical properties of the ester group-containing olefin copolymer microparticles 2 to 5.

<Production Example of Amorphous Resin Fine Particle 1 Dispersion>
- 300 parts of tetrahydrofuran (manufactured by Wako Pure Chemical Industries) - 100 parts of amorphous resin 1 - 0.5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The above materials were weighed, mixed and dissolved.
Next, 20.0 parts of 1 mol/L ammonia water was added, and the ultra-high-speed stirrer T.I. K. The mixture was stirred at 4000 r/min using Robomix (manufactured by Primix). Further, 700 parts of ion-exchanged water was added at a rate of 8 g/min to precipitate amorphous resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion of amorphous resin fine particles 1 having a concentration of 20% (amorphous resin fine particle 1 dispersion).
The volume distribution-based 50% particle size (D50) of the amorphous resin fine particles 1 was 0.13 μm.

<Production Example of Release Agent 1 (Silicone Oil) Fine Particle Dispersion>
・ 100 parts of silicone oil (dimethyl silicone oil manufactured by Shin-Etsu Chemical Co., Ltd.: KF96-500CS kinematic viscosity 500 mm ² /s)
・5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ・395 parts of ion-exchanged water An aqueous dispersion (silicone oil fine particle dispersion) having a concentration of 20% of silicone oil fine particles was obtained by dispersing the silicone oil over time.
The 50% particle diameter (D50) based on volume distribution of the silicone oil fine particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.09 μm.

<Production Example of Release Agent 2 (Aliphatic Hydrocarbon Compound) Fine Particle Dispersion>
・ Aliphatic hydrocarbon compound HNP-51 (manufactured by Nippon Seiro) 100 parts ・ Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 5 parts ・ Ion-exchanged water 395 parts Weigh the above materials and mix with a stirring device After being put into a container, the mixture was heated to 90° C. and circulated to Clearmix W Motion (manufactured by M Technique) for dispersion treatment for 60 minutes. The conditions for distributed processing were as follows.
・Rotor outer diameter 3cm
・Clearance 0.3mm
・Rotor speed 19000r/min
・Screen rotation speed 19000r/min
After the dispersion treatment, cooling to 40 ° C. under the cooling treatment conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 ° C. / min. A dispersion liquid (aliphatic hydrocarbon compound fine particle dispersion liquid) was obtained.
The 50% particle diameter (D50) based on volume distribution of the aliphatic hydrocarbon compound fine particles was measured using a dynamic light scattering particle size distribution meter Nanotrac UPA-EX150 (manufactured by Nikkiso) and found to be 0.15 μm. .

<Production of Colorant Fine Particle Dispersion>
- Colorant 50.0 parts (Cyan pigment made by Dainichiseika: Pigment Blue 15:3)
・Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 7.5 parts ・Ion-exchanged water 442.5 parts Weigh and mix the above materials, dissolve them, and use a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). and dispersed for about 1 hour to obtain an aqueous dispersion (colorant fine particle dispersion) having a concentration of 10% of colorant fine particles in which the colorant is dispersed.
The 50% particle diameter (D50) based on volume distribution of the fine particles of the colorant was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.

<Production Example of Toner 1>
・Ester group-containing olefin copolymer fine particle 1 dispersion: 480 parts ・Silicone oil fine particle dispersion: 125 parts ・Colorant fine particle dispersion: 80 parts ・Ion-exchanged water: 160 parts After mixing, 60 parts of 10% aqueous magnesium sulfate solution were added. Subsequently, the mixture was dispersed at 5000 r/min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). After that, the mixture was heated to 73° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. After holding at 73° C. for 5 minutes, the volume average particle size of the formed aggregated particles is appropriately confirmed using Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. It was confirmed that
After adding 330 parts of a 5% sodium ethylenediaminetetraacetate aqueous solution to the dispersion liquid of the aggregated particles, the mixture was heated to 98° C. while stirring was continued. Then, the aggregated particles were fused by holding at 98° C. for 1 hour.
Thereafter, the temperature was lowered to 50° C. and held for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
After that, as a step of removing divalent metal ions derived from the flocculant, the film was washed with a 5% sodium ethylenediaminetetraacetate aqueous solution while maintaining the temperature at 50°C.
Then, it was cooled to 25° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After washing, the particles were dried using a vacuum dryer to obtain toner particles 1 having a weight average particle size (D4) of about 6.07 μm. The resin existing on the surface of the toner particles 1 was the ester group-containing olefin copolymer 1 .
・Toner particles 1 100 parts ・Inorganic fine particles 1 3 parts ・Small particle size silica particles surface-treated with hexamethyldisilazane having an average particle size of 20 nm 1 part Henschel mixer FM-10C type (manufactured by Mitsui Miike Kakoki Co., Ltd.) Toner 1 was obtained by mixing at a rotational speed of 30 s ⁻¹ and a rotational time of 10 min.
The weight average particle diameter (D4) of Toner 1 was 6.07 μm, and the average circularity was 0.975. Physical properties are shown in Table 4.

<Manufacturing Examples of Toners 2 to 12>
Toners 2 to 12 were obtained in the same manner as in Production Example of Toner 1, except that the ester group-containing olefin copolymer fine particle 1 dispersion and the inorganic fine particles 1 were changed as shown in Table 4. Resins present on the surfaces of toner particles 2 to 12 were ester group-containing olefin copolymers shown in the resin type column of Table 4, respectively. Table 4 shows the physical properties of toners 2 to 12.

<Production Example of Toner 13>
・Amorphous resin fine particle 1 dispersion liquid 480 parts (resin 1 that forms the core)
Aliphatic hydrocarbon compound fine particle dispersion liquid 150 parts Colorant fine particle dispersion liquid 80 parts Ion-exchanged water 160 parts After putting the above materials into a round stainless steel flask and mixing, 60 parts of a 10% magnesium sulfate aqueous solution is added. added. Subsequently, the mixture was dispersed at 5000 r/min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). After that, the mixture was heated to 73° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. After holding at 73° C. for 5 minutes, the volume average particle size of the formed aggregated particles is appropriately confirmed using Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. Then, the material of resin 2 forming the shell below was added over 3 minutes.
・Ester group-containing olefin-based copolymer fine particles 1 dispersion liquid 20 parts After being charged and kept at 73 ° C. for 10 minutes, the volume average particle size of the formed aggregated particles was measured using Coulter Multisizer III, and the weight average particle size. It was confirmed that aggregated particles with (D4) of about 6.07 μm were formed.
After adding 330 parts of a 5% sodium ethylenediaminetetraacetate aqueous solution to the dispersion liquid of the aggregated particles, the mixture was heated to 98° C. while stirring was continued. Then, the aggregated particles were fused by holding at 98° C. for 1 hour.
Thereafter, the temperature was lowered to 50° C. and held for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
After that, as a step of removing divalent metal ions derived from the flocculant, the film was washed with a 5% sodium ethylenediaminetetraacetate aqueous solution while maintaining the temperature at 50°C.
Then, it was cooled to 25° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After washing, the toner particles 13 having a weight average particle size (D4) of about 6.07 μm were obtained by drying using a vacuum dryer. The resin existing on the surface of the toner particles 13 was the ester group-containing olefin copolymer 1 .
・Toner particles 13 100 parts ・Inorganic fine particles 1 3 parts ・Small particle size silica fine particles surface-treated with hexamethyldisilazane having an average particle size of 20 nm 1 part Henschel mixer FM-10C type (manufactured by Mitsui Miike Kakoki Co., Ltd.) The mixture was mixed at a rotational speed of 30 s ⁻¹ for a rotational time of 10 min, and a toner 13 was obtained.
The weight average particle diameter (D4) of toner 13 was 6.07 μm, and the average circularity was 0.975.

<Production Example of Toner 14>
Toner 14 was obtained in the same manner as in Production Example of Toner 13, except that 20 parts of the ester group-containing olefin copolymer fine particle 1 dispersion liquid was changed to 50 parts. The resin present on the surfaces of the toner particles 14 was the ester group-containing olefinic copolymer 1 .

<Production Example of Toner 15>
Toner 15 was obtained in the same manner as in Toner 1 Production Example except that inorganic fine particles 1 were changed to inorganic fine particles 10 . The resin existing on the surfaces of the toner particles 15 was the ester group-containing olefinic copolymer 1 .

<Manufacturing Example of Toner 16>
Toner 16 was obtained in the same manner as in Production Example of Toner 1 except that ester group-containing olefin copolymer fine particles 1 were changed to ester group-containing olefin copolymer fine particles 6 . The resin existing on the surfaces of the toner particles 16 was the ester group-containing olefin copolymer 6 .

<Production Example of Toner 17>
Amorphous resin fine particle 1 dispersion liquid 500 parts Aliphatic hydrocarbon compound fine particle dispersion liquid 150 parts Colorant fine particle dispersion liquid 80 parts After that, 60 parts of a 10% magnesium sulfate aqueous solution was added. Subsequently, the mixture was dispersed at 5000 r/min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). After that, the mixture was heated to 73° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. After holding at 73° C. for 5 minutes, the volume average particle size of the formed aggregated particles is appropriately confirmed using Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. Confirmed that
After adding 330 parts of a 5% sodium ethylenediaminetetraacetate aqueous solution to the dispersion liquid of the aggregated particles, the mixture was heated to 98° C. while stirring was continued. Then, the aggregated particles were fused by holding at 98° C. for 1 hour.
After that, as a step of removing divalent metal ions derived from the flocculant, the film was washed with a 5% sodium ethylenediaminetetraacetate aqueous solution while maintaining the temperature at 50°C.
Then, it was cooled to 25° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After washing, the particles were dried using a vacuum dryer to obtain toner particles 17 having a weight average particle size (D4) of about 6.07 μm. Amorphous resin 1 was present on the surface of toner particles 17 .
・Toner particles 17 100 parts ・Inorganic fine particles 1 3 parts ・Small particle size silica particles surface-treated with hexamethyldisilazane having an average particle size of 20 nm 1 part Henschel mixer FM-10C type (manufactured by Mitsui Miike Kakoki Co., Ltd.) The toner 17 was obtained by mixing at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min.
The weight average particle size (D4) of toner 17 was 6.07 μm, and the average circularity was 0.975.

<Production Example of Toner 18>
・Ester group-containing olefin copolymer fine particle 5 dispersion: 480 parts ・Silicone oil fine particle dispersion: 125 parts ・Colorant fine particle dispersion: 80 parts ・Ion-exchanged water: 160 parts After mixing, 60 parts of 10% aqueous magnesium sulfate solution were added. Subsequently, the mixture was dispersed at 5000 r/min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). After that, the mixture was heated to 73° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. After holding at 73° C. for 5 minutes, the volume average particle size of the formed aggregated particles is appropriately confirmed using Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. It was confirmed that
After adding 330 parts of a 5% sodium ethylenediaminetetraacetate aqueous solution to the dispersion liquid of the aggregated particles, the mixture was heated to 98° C. while stirring was continued. Then, the aggregated particles were fused by holding at 98° C. for 1 hour.
Thereafter, the temperature was lowered to 50° C. and held for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
After that, as a step of removing divalent metal ions derived from the flocculant, the film was washed with a 5% sodium ethylenediaminetetraacetate aqueous solution while maintaining the temperature at 50°C.
Then, it was cooled to 25° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After washing, the toner particles 18 having a weight average particle size (D4) of about 6.07 μm were obtained by drying using a vacuum dryer. The resin existing on the surfaces of the toner particles 18 was the ester group-containing olefin copolymer 5 .
・Toner particles 18 100 parts ・Inorganic fine particles 1 3 parts ・Small particle size silica particles surface-treated with hexamethyldisilazane having an average particle size of 20 nm 1 part Henschel mixer FM-10C type (manufactured by Mitsui Miike Kakoki Co., Ltd.) The toner 18 was obtained by mixing at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min.
The weight average particle size (D4) of toner 18 was 6.07 μm, and the average circularity was 0.975.

<Production Example of Toner 19>
・Ester group-containing olefin copolymer fine particle 1 dispersion 230 parts ・Amorphous resin 1 fine particle dispersion 250 parts ・Silicone oil fine particle dispersion 125 parts ・Colorant fine particle dispersion 80 parts ・Ion-exchanged water 160 parts After each material was put into a round stainless steel flask and mixed, 60 parts of a 10% magnesium sulfate aqueous solution was added. Subsequently, the mixture was dispersed at 5000 r/min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). After that, the mixture was heated to 73° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. After holding at 73° C. for 5 minutes, the volume average particle size of the formed aggregated particles is appropriately confirmed using Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. It was confirmed that
After adding 330 parts of a 5% sodium ethylenediaminetetraacetate aqueous solution to the dispersion liquid of the aggregated particles, the mixture was heated to 98° C. while stirring was continued. Then, the aggregated particles were fused by holding at 98° C. for 1 hour.
Thereafter, the temperature was lowered to 50° C. and held for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
After that, as a step of removing divalent metal ions derived from the flocculant, the film was washed with a 5% sodium ethylenediaminetetraacetate aqueous solution while maintaining the temperature at 50°C.
Then, it was cooled to 25° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After washing, the toner particles 19 having a weight average particle size (D4) of about 6.07 μm were obtained by drying using a vacuum dryer. On the surface of the toner particles 19, the amorphous resin 1 and the ester group-containing olefin copolymer fine particles 1 were mixed.
・Toner particles 19 100 parts ・Inorganic fine particles 1 3 parts ・Small particle size silica particles surface-treated with hexamethyldisilazane having an average particle size of 20 nm 1 part Henschel mixer FM-10C type (manufactured by Mitsui Miike Kakoki Co., Ltd.) The mixture was mixed at a rotation speed of 30 s ⁻¹ and a rotation time of 10 minutes to obtain Toner 19 .
The weight average particle size (D4) of toner 19 was 6.07 μm, and the average circularity was 0.975.

<Production Example of Toner 20>
・Ester group-containing olefin copolymer fine particle 1 dispersion: 480 parts ・Silicone oil fine particle dispersion: 125 parts ・Colorant fine particle dispersion: 80 parts ・Ion-exchanged water: 160 parts After mixing, 60 parts of 10% aqueous magnesium sulfate solution was added. Subsequently, the mixture was dispersed at 5000 r/min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). After that, the mixture was heated to 73° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. After holding at 73° C. for 5 minutes, the volume average particle size of the formed aggregated particles is appropriately confirmed using Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. It was confirmed that
After adding 330 parts of a 5% sodium ethylenediaminetetraacetate aqueous solution to the dispersion liquid of the aggregated particles, the mixture was heated to 98° C. while stirring was continued. Then, the aggregated particles were fused by holding at 98° C. for 1 hour.
Thereafter, the temperature was lowered to 50° C. and held for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
After that, as a step of removing divalent metal ions derived from the flocculant, the film was washed with a 5% sodium ethylenediaminetetraacetate aqueous solution while maintaining the temperature at 50°C.
Then, it was cooled to 25° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After washing, the toner particles 20 having a weight average particle size (D4) of about 6.07 μm were obtained by drying using a vacuum dryer. The resin existing on the surface of the toner particles 20 was the ester group-containing olefin copolymer 1 .
・Toner particles 20 100 parts ・Inorganic fine particles 11 (large particle diameter spherical silica fine particles surface-treated with hexamethyldisilazane having an average particle diameter of 100 nm) 3 parts ・Small particle diameter particles surface-treated with hexamethyldisilazane having an average particle diameter of 20 nm Fine silica particles 1 part Each of the above materials was mixed in a Henschel mixer FM-10C (manufactured by Mitsui Miike Kakoki Co., Ltd.) at a rotation speed of 30 s ⁻¹ for a rotation time of 10 minutes to obtain toner 20 .
The weight average particle diameter (D4) of toner 20 was 6.07 μm, and the average circularity was 0.975.

<Manufacturing Example of Toner 21>
・Ester group-containing olefin copolymer fine particle 1 dispersion: 480 parts ・Silicone oil fine particle dispersion: 125 parts ・Colorant fine particle dispersion: 80 parts ・Ion-exchanged water: 160 parts After mixing, 60 parts of 10% aqueous magnesium sulfate solution was added. Subsequently, the mixture was dispersed at 5000 r/min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). After that, the mixture was heated to 73° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. After holding at 73° C. for 5 minutes, the volume average particle size of the formed aggregated particles is appropriately confirmed using Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. It was confirmed that
After adding 330 parts of a 5% sodium ethylenediaminetetraacetate aqueous solution to the dispersion liquid of the aggregated particles, the mixture was heated to 98° C. while stirring was continued. Then, the aggregated particles were fused by holding at 98° C. for 1 hour.
Thereafter, the temperature was lowered to 50° C. and held for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
After that, as a step of removing divalent metal ions derived from the flocculant, while maintaining at 50 ° C., 5
% ethylenediaminetetrasodium acetate aqueous solution.
Then, it was cooled to 25° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After washing, the toner particles 21 having a weight average particle size (D4) of about 6.07 μm were obtained by drying using a vacuum dryer. The resin existing on the surface of the toner particles 21 was the ester group-containing olefin copolymer 1 .
・Toner particles 21 100 parts ・Inorganic fine particles 12 (needle-shaped titanium oxide fine particles surface-treated with hexamethyldisilazane having an average particle size of 50 nm) 3 parts ・Small particle size silica surface-treated with hexamethyldisilazane having an average particle size of 20 nm Fine particles 1 part Each of the above materials was mixed in a Henschel mixer FM-10C (manufactured by Mitsui Miike Kakoki Co., Ltd.) at a rotation speed of 30 s ⁻¹ for a rotation time of 10 minutes to obtain toner 21 .
The weight average particle diameter (D4) of toner 21 was 6.07 μm, and the average circularity was 0.975.

<Production Example of Magnetic Core Particle 1>
- Process 1 (weighing/mixing process):
Fe ₂ O ₃ 62.7 parts MnCO ₃ 29.5 parts Mg(OH) ₂ 6.8 parts SrCO ₃ 1.0 parts Ferrite raw materials were weighed so as to achieve the above composition ratio. After that, it was pulverized and mixed for 5 hours in a dry vibration mill using stainless steel beads having a diameter of 1/8 inch.
・Step 2 (temporary firing step):
The obtained pulverized material was made into pellets of about 1 mm square by a roller compactor. Coarse powder was removed from the pellets with a vibrating sieve with an opening of 3 mm, and then fine powder was removed with a vibrating sieve with an opening of 0.5 mm. 01% by volume) and fired at a temperature of 1000° C. for 4 hours to produce a calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393
・Step 3 (crushing step):
After crushing the obtained calcined ferrite to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of calcined ferrite using zirconia beads with a diameter of 1/8 inch, and the mixture was crushed with a wet ball mill for 1 hour. . The obtained slurry was pulverized for 4 hours in a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (fine pulverized product of calcined ferrite).
- Step 4 (granulation step):
To the ferrite slurry, 1.0 parts of ammonium polycarboxylate as a dispersing agent and 2.0 parts of polyvinyl alcohol as a binder are added to 100 parts of calcined ferrite, and a spray dryer (manufacturer: Okawara Kakoki) is used to form spherical particles. Granulated. After adjusting the particle size of the obtained particles, they were heated at 650° C. for 2 hours using a rotary kiln to remove the organic components of the dispersant and binder.
- Step 5 (firing step):
In order to control the sintering atmosphere, the temperature was raised from room temperature to 1300° C. in 2 hours in an electric furnace under a nitrogen atmosphere (oxygen concentration 1.00% by volume), and then sintered at 1150° C. for 4 hours. After that, the temperature was lowered to 60° C. over 4 hours, the nitrogen atmosphere was returned to the air, and the temperature was 40° C. or less and taken out.
・Step 6 (sorting step):
After crushing the aggregated particles, the low magnetic force products are cut by magnetic separation, sieved with a sieve with an opening of 250 μm to remove coarse particles, and the 50% particle size (D50) of 37.0 μm based on volume distribution. A magnetic core particle 1 was obtained.

<Preparation of Coating Resin 1>
Cyclohexyl methacrylate monomer 26.8 parts Methyl methacrylate monomer 0.2 parts Methyl methacrylate macromonomer 8.4 parts (a macromonomer having a methacryloyl group at one end and a weight average molecular weight of 5000)
toluene 31.3 parts methyl ethyl ketone 31.3 parts azobisisobutyronitrile 2.0 parts The mixture was placed in a four-necked separable flask equipped with a nitrogen inlet tube and a stirrer, and nitrogen gas was introduced to create a nitrogen atmosphere. Thereafter, the mixture was heated to 80° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reactant to precipitate the copolymer, and the precipitate was separated by filtration and dried in vacuum to obtain Coating Resin 1.
Then, 30 parts of coating resin 1 was dissolved in 40 parts of toluene and 30 parts of methyl ethyl ketone to obtain polymer solution 1 (solid content: 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content concentration 30%) 33.3 parts Toluene 66.4 parts Carbon black Regal 330 (manufactured by Cabot) 0.3 parts (primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² /g, DBP oil absorption 75mL/100g)
was dispersed with a paint shaker for 1 hour using zirconia beads with a diameter of 0.5 mm. The resulting dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Manufacturing Example of Magnetic Carrier 1>
(Resin coating step):
The magnetic core particles 1 and the coating resin solution 1 were put into a vacuum degassing kneader maintained at room temperature (the amount of the coating resin solution added was 2.5 parts as a resin component for 100 parts of the magnetic core particles 1). portion). After charging, the mixture was stirred for 15 minutes at a rotation speed of 30 r/min, and after the solvent was volatilized to a certain extent (80% by mass), the mixture was heated to 80°C while mixing under reduced pressure, toluene was distilled off over 2 hours, and then the mixture was cooled. . The obtained magnetic carrier is separated into low magnetic products by magnetic separation, passed through a sieve with an opening of 70 μm, and then classified by an air classifier to obtain a magnetic carrier having a 50% particle size (D50) of 38.2 μm based on volume distribution. got 1.

<Production example of two-component developer 1>
92.0 parts of the magnetic carrier 1 and 8.0 parts of the toner 1 were mixed with a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a two-component developer 1.

<Production Examples of Two-Component Developers 2 to 19>
Two-component developers 2-19 were obtained in the same manner as in Production Example of Two-component Developer 1, except that Toner 1 was changed to Toners 2-19.

<Example 1>
Using the two-component developer 1, the following evaluation was performed.
As an image forming apparatus, a modified imageRUNNER ADVANCE C5560 digital commercial printing printer manufactured by Canon was used, and two-component developer 1 was placed in the developing device at the cyan position. As modifications of the apparatus, the fixing temperature, process speed, DC voltage V _DC of the developer carrier, charging voltage V _D of the electrostatic latent image carrier, and laser power were changed so that they could be set freely. In the image output evaluation, an FFh image (solid image) having a desired image ratio is output, and V _DC , V _D and laser power are adjusted so that the toner amount of the FFh image is desired. did FFh is a value representing 256 gradations in hexadecimal, where 00h is the first gradation (white background portion) of the 256 gradations, and FFh is the 256th gradation (solid portion) of the 256 gradations. .
Evaluation was made based on the following evaluation methods, and the results are shown in Table 5.

[Transferability]
Paper: CS-680 (68.0 g/m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.35 mg/cm ² (FFh image)
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: Place a 2 cm x 5 cm image in the center of the above A4 paper Test environment: High temperature and high humidity environment (temperature 30 ° C./humidity 80% RH (hereinafter H/H))
Process speed: 377mm/sec
Fixing temperature: 180°C
As a stabilization and durability evaluation of the evaluation machine, 30,000 sheets of A4 paper were output using a band chart with an image ratio of 0.1%. After that, the evaluation image was formed on the electrostatic latent image carrier, and the evaluation machine was stopped before the image was transferred to the intermediate transfer member and to the recording paper. The intermediate transfer member of the stopped evaluation machine was taken out, a transparent adhesive tape was attached to the transferred image, the toner was collected, and the adhesive tape was attached to the recording paper. The density of the image was measured with an optical density system, and the transfer density A was obtained by subtracting the density of the portion where only the adhesive tape was applied to the recording paper.
Further, the electrostatic latent image bearing member of the evaluation machine was taken out, and the transfer residual density B was obtained by the same method for the transfer residual toner.
The adhesive tape used was a transparent and weakly adhesive Super Stick (manufactured by Lintec), and the optical densitometer used was an X-Rite color reflection densitometer (manufactured by X-Rite). Then, the transfer efficiency was calculated using the following formula. The obtained transfer efficiency was evaluated according to the following evaluation criteria. When the results were A to C, it was evaluated as having the effects of the present invention.
Transfer efficiency = {transfer density A/(transfer density A + residual transfer density B)} x 100
(Evaluation criteria)
A: Transfer efficiency of 98.0% or more B: Transfer efficiency of 95.0% or more and less than 98.0% C: Transfer efficiency of 90.0% or more and less than 95.0% D: Transfer efficiency of less than 90.0%

[Electrification stability]
Paper: CS-680 (68.0 g/m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.35 mg/cm ² (FFh image)
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: Place a 2 cm x 5 cm image in the center of the above A4 paper Test environment: High temperature and high humidity environment (temperature 30 ° C./humidity 80% RH (hereinafter H/H))
Process speed: 377mm/sec
As a durability evaluation of the evaluation machine, 30,000 sheets of A4 paper were output using an image chart with an image ratio of 40%. Thereafter, the toner charge amount of the durable developer was measured by the measurement method described below, and compared with the toner charge amount before the image durability test.
The charge amount of the toner was measured with an Espart analyzer manufactured by Hosokawa Micron Corporation. The Espart analyzer is a device that introduces sample particles into a detection unit (measuring unit) in which an electric field and an acoustic field are formed simultaneously, measures the moving speed of the particles by the laser Doppler method, and measures the particle size and charge amount. . A sample particle that has entered the measurement section of the device is affected by the acoustic field and the electric field, and falls while being deflected in the horizontal direction, and the beat frequency of this horizontal velocity is counted. The count value is input to the computer by interruption, and the particle size distribution or the charge amount distribution per unit particle size is displayed on the computer screen in real time. Then, when the charge amount for a predetermined number is measured, the screen stops, and after that, the three-dimensional distribution of the charge amount and particle size, the charge amount distribution by particle size, the average charge amount (coulomb/weight), etc. are displayed on the screen. to be displayed.
The charging amount of the toner was measured by introducing the above two-component developer as sample particles into the measurement section of the Espart analyzer.
The measurement result was substituted into the following formula to calculate the retention rate of the charge amount of the toner, which was evaluated according to the following criteria. Table 5 shows the evaluation results. When the results were A to C, it was evaluated as having the effects of the present invention.
Formula: Toner triboelectric charge retention rate (%)
= [toner charge amount of the durable developer]/[toner charge amount of the initial developer] x 100
(Evaluation criteria)
A: Charge retention rate of toner is 95% or more B: Charge retention rate of toner is 90% or more and less than 95% C: Charge retention rate of toner is 80% or more and less than 90% D: Charge retention rate of toner is less than 80%

Claims (10)

A toner having toner particles and inorganic fine particles,
The resin present on the surface of the toner particles has a displacement h of 300 nm to 500 nm when a load of 50 μN is applied in an environment of 25° C., as measured by an ultra-microhardness measuring device, and is plastically deformed. The rate H is 1.0% to 30.0%,
The inorganic fine particles have a rectangular parallelepiped particle shape,
the inorganic fine particles are strontium titanate,
The resin present on the surface of the toner particles contains 50% by mass or more of an ester group-containing olefin copolymer,
The toner, wherein the ester group-containing olefinic copolymer has an ester group concentration of 2.0% by mass to 17.9% by mass with respect to the total mass of the ester group-containing olefinic copolymer. . 2. The toner according to claim 1, wherein the resin existing on the surface of the toner particles is present in a region of 0 nm to 100 nm from the outer surface of the toner particles toward the center. The inorganic fine particles are surface-treated with a surface treatment agent,
3. The toner according to claim 1, wherein the solubility parameter (SP1) of the resin present on the surface of the toner particles and the solubility parameter (SP2) of the surface treatment agent satisfy the following formula (1).
|SP1−SP2|≦1.00 (1) 4. The toner according to any one of claims 1 to 3, wherein a surface potential B obtained in a rubbing test using the inorganic fine particles and the resin present on the surface of the toner particles is 100 V or higher.
Surface potential B=(Surface potential D of the resin pieces measured in a state where the inorganic fine particles adhere to the resin pieces after rubbing the resin pieces of the resin present on the surface of the toner particles with the inorganic fine particles)- (Surface potential E measured using a resin piece obtained by removing the inorganic fine particles by air blow after rubbing the resin pieces of the resin present on the surface of the toner particles with the inorganic fine particles) Claims 1 to 3, wherein the primary particles of the inorganic fine particles have a number average particle size of 10 nm to 250 nm
5. The toner according to any one of 4. The ester group-containing olefin-based copolymer is
a unit Y1 represented by the following formula (2);
6. The toner according to any one of claims 1 to 5, further comprising at least one unit Y2 selected from the group of units represented by the following formula (3) and units represented by the following formula (4). .

(wherein R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , R ⁴ represents H or CH ₃ , R ⁵ represents indicates _CH3 or _C2H5 . ₎ The toner according to any one of claims 1 to 6, wherein the inorganic fine particles have a cubic particle shape. The toner according to any one of claims 1 to 7, wherein the displacement h of the resin present on the surface of the toner particles is 400-480 nm. The toner according to any one of claims 1 to 8, wherein the plastic deformation rate H of the resin present on the surface of the toner particles is 1.0 to 15.0%. A method for producing the toner according to any one of claims 1 to 9 ,
The manufacturing method is
a dispersion step of adjusting a resin fine particle dispersion;
an aggregating step of aggregating the resin fine particle dispersion to form an aggregate; and
A method for producing a toner, comprising a fusing step of heating and fusing the aggregates.

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