JP2020034598A - Toner and manufacturing method of toner - Google Patents

Abstract

To provide toner capable of maintaining excellent transferability and charging stability in a long-term image output.SOLUTION: There are provided toner including toner particles and inorganic fine particles and a manufacturing method of toner. The toner particles have a resin on the surface thereof, the displacement h of which when a load of 50 μN is applied under a 25°C environment is 300 nm to 500 nm measured by a micro-hardness measuring device, the plastic deformation rate H is 1.0% to 30.0%, and the inorganic fine particles have a rectangular particle shape.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and the like, and a method for manufacturing the toner.

In recent years, with the widespread use of electrophotographic full-color copiers, the added value of improving serviceability such as maintenance costs, such as higher speed, higher image quality, color stability, and maintenance-free performance, as well as higher speed. Improvement is also required.
Specifically, a toner that does not deteriorate even in long-term image output is required as a toner that achieves improved maintenance performance.
Therefore, as a toner that is unlikely to deteriorate even in long-term image output, a proposal has been made to add inorganic fine particles having a large particle diameter to the toner surface to exhibit a spacer effect (Patent Document 1). Further, 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

In the initial image output, the toner described in Patent Document 1 reduces the adhesion of the toner due to the spacer effect caused by the inorganic fine particles, so that high-quality image output with good developability and transferability is possible. Has become.
However, since the toner described in Patent Document 1 uses polyester or styrene acrylic resin as a binder resin, non-fine particles having a large particle diameter are buried in the toner surface due to stirring of a developing device in long-term image output. In some cases. As a result, the spacer effect is reduced and the adhesion of the toner is increased, so that the transfer efficiency is reduced and the image density may be reduced. That is, in long-term image output, maintenance such as replacement of the developer may be required.
On the other hand, in the toner described in Patent Document 2, even in a long-term image output, burying of the inorganic fine particles is suppressed by rubber elasticity, and a reduction in the adhesive force of the toner is maintained. However, since the rubber elasticity is strong, the inorganic fine particles attached to the toner surface are easily detached, and the inorganic fine particles may contaminate the toner carrier (carrier) of the two-component developer and the charging member. As a result, the charging stability is reduced to cause an image defect, or a vertical stripe-like stain is generated on the paper surface, so that maintenance such as replacement of a developer or a charging member may be required.
From the above, there is a trade-off relationship between suppression of burying of inorganic fine particles and suppression of desorption, and development of a toner that breaks this trade-off relationship and maintains excellent transferability and charging stability in long-term image output. Is urgently needed.

The toner of the present invention is a toner having toner particles and inorganic fine particles,
The resin existing 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 under an environment of 25 ° C., which is measured by a micro-hardness measuring device, and has a plastic deformation. Rate H is 1.0% to 30.0%,
The inorganic fine particles have a rectangular parallelepiped particle shape.

Further, the method for producing a toner of the present invention is a method for producing a toner of the present invention,
The production method
A dispersion step of preparing a resin fine particle dispersion,
An aggregation step of aggregating the resin fine particle dispersion to form an aggregate, and
The method is characterized by comprising a fusion step of heating and aggregating the aggregate.

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

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

  In the present invention, description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit, which are endpoints, unless otherwise specified.

The toner of the present invention is a toner having toner particles and inorganic fine particles,
The resin existing 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 under an environment of 25 ° C., which is measured by a micro-hardness measuring device, and has a plastic deformation. Rate H is 1.0% to 30.0%,
The inorganic fine particles have 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 under an environment of 25 ° C., which is measured by an ultra-micro hardness measuring device, is defined as one particle of toner in a developing device of an actual machine It is based on the fact that the maximum load applied to is 50 μN derived by simulation or the like.

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

As long as the resin existing on the surface of the toner particles has the mechanical properties described below. The toner particles may have a core-shell structure in which the surface is a shell layer, or may include a resin having the same mechanical properties on the surface of the toner particles and the inside of the toner particles.
The state 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, and the like in the core-shell formation using the emulsion aggregation method described below. be able to.
As a method of controlling the state of the resin present on the surface of the toner particles other than the emulsification aggregation method, for example, by dispersing a mixture in which a toner constituent material described below is dissolved or dispersed in a water-insoluble organic solvent in an aqueous medium. "Dissolution suspension method" in which the toner particles are granulated. In the dissolution suspension method, by increasing the affinity between a resin having mechanical properties described below and an aqueous medium, specifically, by increasing the solubility parameter described below, the resin spontaneously forms toner particles. Can be localized on the surface.

When the displacement h of the resin is 300 nm to 500 nm when a load of 50 μN is applied under an environment of 25 ° C. measured by an ultra-micro hardness measuring device, the resin acts as a cushion material. The load applied to one particle can be absorbed by the resin, the burying of the inorganic fine particles in the toner particles can be suppressed, and the transferability is improved. The displacement h is preferably from 350 nm to 490 nm, more preferably from 400 nm to 480 nm.
On the other hand, when the displacement h is less than 300 nm, the displacement at the time of applying the maximum load received in the developing machine is small, so that the load applied to one toner particle cannot be sufficiently absorbed, and the inorganic fine particles are easily buried. , Transferability is reduced. Further, when the displacement h is larger than 500 nm, the melting point of the resin material is reduced due to the material design. Therefore, in a long-term image output under a high temperature and high humidity environment, the resin is easily melted and deformed, and the inorganic fine particles are easily buried. And the transferability decreases.
The displacement h can be adjusted by appropriately changing the ester group concentration and the molecular weight of the resin existing on the surface of the toner particles described later.

When the plastic deformation rate H of the resin when a load of 50 μN is applied under an environment of 25 ° C., which is measured by a micro-hardness measuring device, is 1.0% to 30.0%, It means that the resin existing on the surface is hardly plastically deformed even when the maximum load received in the developing machine is applied, that is, it has rubber elasticity. As a result, burying 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%, and 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 material is reduced due to the material design, so that the resin is easily melted and deformed in a long-term image output under a high-temperature and high-humidity environment. Fine particles are easily buried and transferability is reduced. On the other hand, when the plastic deformation rate H is larger than 30.0%, sufficient rubber elasticity capable of suppressing the burying of the inorganic fine particles is not exhibited, so that the inorganic fine particles are easily buried and the transferability is reduced.
The plastic deformation rate H can be adjusted by appropriately changing the ester group concentration and the molecular weight of the resin existing on the surface of the toner particles described later.

The present inventors have conducted intensive studies and found that the toner particles having the resin on the surface can suppress the embedding of the inorganic fine particles added to the toner particles due to the viscoelastic properties of the resin, but the conventional amorphous It has been found that there is a problem that the inorganic fine particles are more easily detached from the toner particles than a toner having a resin on the surface.
That is, only by appropriately controlling the viscoelasticity of the resin existing on the surface of the toner particles, there is a trade-off relationship between the suppression of the burying of the inorganic fine particles and the suppression of the desorption thereof. Therefore, there is room for improvement of the toner that breaks this trade-off relationship and can maintain excellent transferability and charging stability in long-term image output.

Therefore, the present inventors have studied not only the viscoelastic properties of the resin existing on the surface of the toner particles but also the shape of the inorganic fine particles. As a result, it has been found that when the inorganic fine particles have a rectangular parallelepiped particle shape, the inorganic fine particles are hardly detached 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, and the contact area between the toner particles and the inorganic fine particles is larger than that of the spherical fine particles, so that the friction coefficient between the toner particle surface and the inorganic fine particle surface is increased. It is thought that this is because the resistance when detaching is greatly increased.

The inorganic fine particles have a rectangular parallelepiped particle shape. When the particles have a rectangular parallelepiped shape, for example, in the step of attaching the inorganic fine particles to the toner particles, the inorganic fine particles are easily fixed 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 the rectangular particle shapes.
The cubic shape and the cuboid shape are not limited to a perfect cubic shape and a cuboid shape, respectively, and include, for example, a substantially cubic shape and a substantially cuboid shape in which corners are partially missing or rounded.
The aspect ratio of the inorganic fine particles having a rectangular parallelepiped particle shape is preferably from 1.0 to 3.0.

  The inorganic fine particles are not particularly limited as long as they have a rectangular parallelepiped particle shape, but titanates are preferred because they can be easily controlled into cubic particle shapes. Specific examples of titanates include, for example, barium titanate, aluminum titanate, magnesium titanate, calcium titanate, strontium titanate and the like. 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 having a perovskite crystal structure can be produced mainly in an aqueous medium without going through a sintering step. Production in an aqueous medium is preferable because it can be easily controlled to a uniform particle size.
That is, strontium titanate having a rectangular parallelepiped particle shape and having a perovskite-type crystal structure is such that a resin having rubber elasticity remains on the toner particle surface in a state in which the resin is hardly detached from the toner particles existing on the surface of the toner particle. Is possible. Since the toner particles have the rubber elasticity as described above and have a higher tackiness than the amorphous resin conventionally used in the toner, when the inorganic fine particles come into surface contact with the surface of the toner particles, Develops a very high coefficient of friction. As a result, the inorganic fine particles are unlikely to be detached from the surface of the toner particles, and even when subjected to mechanical stress, the state in which the inorganic particles are difficult to be buried inside the toner particles due to the rubber elasticity of the resin can be achieved. Therefore, excellent transferability and charging stability can be maintained in long-term image output.

The strontium titanate can be obtained, for example, by a normal pressure heating reaction method. Hereinafter, the atmospheric pressure heating reaction method will be described, but the method is not limited thereto.
In the production of strontium titanate by a normal pressure heating reaction method, a mineral acid peptized product of a hydrolyzate of a titanium compound can be used as a titanium oxide source. As the mineral acid peptized product, a product obtained by peptizing metatitanic acid obtained by a sulfuric acid method 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 efficiently peptizing.
As the strontium oxide source, metal nitrates and hydrochlorides can be used. For example, strontium nitrate and strontium chloride can be used. Then, strontium titanate can be produced by mixing the respective solutions containing titanium or strontium, reacting them at 60 ° C. or higher while adding an aqueous alkali solution, and then performing acid treatment.
As the alkaline aqueous solution, caustic alkali can be used, and among them, an aqueous sodium hydroxide solution is preferable.
In the above production method, 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 titanium oxide source concentration at the beginning of the reaction, and the addition of an aqueous alkali solution. Temperature and the rate of addition.
In order to prevent the formation of carbonate in the reaction process, it is preferable to prevent carbon dioxide gas from being mixed, for example, by reacting in a nitrogen gas atmosphere.

The mixing ratio of the titanium oxide source and strontium oxide source during the reaction, a molar ratio of SrO / TiO _2, preferably 0.90 to 1.40, more preferably a 1.05 to 1.20. The concentration of the titanium oxide source at the beginning of the reaction is preferably 0.05 mol / L to 1.30 mol / L as TiO ₂ , more preferably 0.08 mol / L to 1.00 mol / L.
When the temperature at which the alkaline aqueous solution is added exceeds 100 ° C., a pressure vessel such as an autoclave is required, so that the temperature can be practically in the range of 60 ° C. to 100 ° C. As for the addition rate of the aqueous alkali solution, the slower the addition rate, the larger the particle size of the metal titanate particles can be obtained, and the faster the addition rate, the smaller the particle size of the metal titanate particles. The addition rate of the aqueous alkali solution is preferably 0.001 equivalent / h to 1.200 equivalent / h, more preferably 0.002 equivalent / h to 1.100 equivalent / h, based on the charged raw materials.
After obtaining the strontium titanate particles by a heating reaction under normal pressure, it is preferable to further perform an acid treatment in order to remove an unreacted metal source.
In the acid treatment, the pH can be adjusted to preferably 2.5 to 7.0, more preferably 4.5 to 6.0, using hydrochloric acid. As the acid, nitric acid, acetic acid and the like can be used for the acid treatment in addition to hydrochloric acid.

<Surface potential B>
The surface potential B when performing a rubbing test using the inorganic fine particles and the resin present on the surface of the toner particles is preferably 100 V or more, and more preferably 150 V to 400 V. 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 surface treatment of the inorganic fine particles is performed. When the surface potential B is in the range of 100 V or more, detachment of the inorganic fine particles from the surface of the toner particles is further suppressed, and as a result, transferability is further improved.

The inorganic fine particles may be surface-treated with a surface treating agent. The surface treatment agent is not particularly limited, and examples thereof include a disilylamine compound, a halogenated silane compound, a silicone compound, and a silane coupling agent.
The disilylamine compound is a compound having a disilylamine (Si-N-Si) site. Examples of the disilylamine compound include, for example, hexamethyldisilazane (HMDS), N-methyl-hexamethyldisilazane, and hexamethyl-N-propyldisilazane. Examples of the halogenated silane compound include, for example, dimethyldichlorosilane.
Examples of the silicone compound include, for example, silicone oil or silicone resin (varnish). Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. Examples of the silicone resin (varnish) include methyl silicone varnish and phenylmethyl silicone varnish.
Examples of the silane coupling agent include, for example, a silane coupling agent having an alkyl group and an alkoxy group, a silane coupling agent having an amino group and an alkoxy group, and a fluorine-containing silane coupling agent. More specifically as the silane coupling agent, 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- Such as Li fluorohexyl diethoxy silane.
The surface treatment agent may be used alone 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 treating agent used for the inorganic fine particles preferably satisfy the following formula (1). More preferably, 1 ′) is satisfied.
| SP1−SP2 | ≦ 1.00 (1)
0.03 ≦ | SP1-SP2 | ≦ 0.85 (1 ′)
The SP values (SP1 and SP2) can be obtained using the Fedors equation. Here, the values of Δei and Δvi are calculated based on the evaporation energy and the molar volume of the atoms and atomic groups according to Table 3-9 described on pages 54 to 57 of “Basic Science of Coating” (1986 (Maki Shoten)). 25 ° C.).
Formula: δi = [Ev / V] ^1/2 = [Δei / Δvi] ^1/2
Ev: Evaporation energy V: Molar volume Δei: Evaporation energy of atom or atomic group of i component Δvi: Molar volume of atom or atomic group of i component

For example, the SP value of a resin composed of ethylene and norbornene and having a copolymerization ratio of 1: 1 is composed of an atomic group (a ring structure of -5 or more members) × 1 + (— CH ₂ ) × 3 as a repeating unit. , SP values are determined by the following equations.
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, the detachment of the inorganic fine particles from the surface of the toner particles can be further suppressed.

<Addition amount of inorganic fine particles>
The inorganic fine particles having a rectangular parallelepiped particle shape are preferably used in an amount of 0.1 parts by mass to 20.0 parts by mass, more preferably 0.1 parts by mass, based on 100 parts by mass of the toner particles, from the viewpoint of charging stability. It is from 1 part 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 from 10 nm to 250 nm. When the particle diameter is 250 nm or less, the separation of the toner particles from the surface can be suppressed when the toner particles and the inorganic fine particles are mixed during the production of the toner. When the particle size is 10 nm or more, the spacer effect of the inorganic fine particles is exhibited, and thus the transferability is improved. Above all, from the viewpoint that the inorganic fine particles can be more uniformly and firmly attached, the thickness is more preferably from 20 to 100 nm, further preferably from 30 to 100 nm.

In addition to the above-described inorganic fine particles having a rectangular parallelepiped particle shape, other inorganic fine powders may be contained in the toner particles as needed. The inorganic fine powder may be internally added to the toner particles, or may be mixed with the toner particles as an external additive.
As the external additive, inorganic fine powder such as silica, titanium oxide and aluminum oxide is preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil and a mixture thereof.
As the external additive for improving the fluidity, the inorganic fine powder is preferably a specific surface area of ^{50m 2} / ^g~400m 2 / g, as the external additive for durable stability, specific surface area of ^{10 m} 2 / g It is preferable that the inorganic fine powder is at least 50 m ² / g. In order to achieve both improvement in fluidity and stability of durability, an inorganic fine powder having a specific surface area in 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 based on 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer can be used for mixing the toner particles and the external additive.

  The mixing of the toner particles and the inorganic fine particles can be performed using a known mixer such as a Henschel mixer, a mechano hybrid (manufactured by Nippon Coke Co., Ltd.), a super mixer, and a nobilta (manufactured by Hosokawa Micron Corporation). Absent.

<Resin on the surface of toner particles>
The resin present on the surface of the toner particles preferably contains the ester group-containing olefin copolymer in an amount of 50% by mass or more, more preferably more than 50% by mass, and more preferably 70% by mass to 100% by mass. More preferably, it is contained by mass%. As a result, the resin present on the surface of the toner particles exhibits appropriate rubber elasticity, and can maintain more excellent transferability in long-term image output.
When the resin present on the surface of the toner particles contains 50% by mass or more of the ester group-containing olefin-based copolymer, the main component of the resin present on the surface of the toner particles becomes an elastomer resin having a low glass transition temperature. Therefore, the resin existing on the surface of the toner particles easily functions as a cushioning agent, and the burying of the inorganic fine particles can be further suppressed.

Further, the ester group-containing olefin 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). It is preferable to have at least one type of unit Y2. In this case, the resin existing on the surface of the toner particles easily develops rubber elasticity, and more excellent transferability can be maintained in long-term image output.
In the above case, since the main component of the resin present on the surface of the toner particles is an elastomer resin having a low glass transition temperature, the resin existing on the surface of the toner particles easily functions as a cushioning agent, and the inorganic fine particles are buried. Can be further suppressed.

(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 , and R ⁵ represents CH ₃ or C ₂ H ₅ is shown.)

Hereinafter, at least one unit Y1 selected from the group of the unit represented by the formula (2) and the unit represented by the formula (3) will be specifically described.
When the ester group-containing olefin-based copolymer is any of the following compounds, the melting point of the ester group-containing olefin-based copolymer is lower than the melting point of polyethylene, so that better low-temperature fixability can be obtained.
Further, since the ester group-containing olefin-based copolymer acts as an elastomer to easily exhibit rubber elasticity, it is possible to further suppress the burying of the inorganic fine particles.
Furthermore, a polar group ester group can be contained in polyethylene having a high volume resistance, so that the volume resistance can be reduced to a considerable extent, and the localization of electric charges due to triboelectric charging can be suppressed. As a result, the electrostatic adhesion between the intermediate transfer member and the toner can be reduced, so that better transferability can be obtained.
(I) In the unit represented by the formula (2) and the unit represented by the formula (3), ethylene is a copolymer in which R ¹ is H, R ² is H, and R ³ is CH _3. -Vinyl acetate copolymer (ii) In the unit represented by the formula (2) and the unit represented by the formula (4), ethylene-acryl wherein R ¹ is H, R ⁴ is H, and R ⁵ is CH ₃ Acid methyl 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 formula (2) and the unit represented by the formula (4) (Vi) Ethylene-ethyl acrylate copolymer (v) In the units represented by the formulas (2) and (4), ethylene wherein R ¹ is H, R ⁴ is CH ₃ , and R ⁵ is CH ₃ -Methyl methacrylate copolymer

  The ester group-containing olefin copolymer has a total mass of the ester group-containing olefin copolymer of Z1, a mass of the unit represented by the formula (2), the formula (3), or the formula (4) of 1, 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, and 0.95 to 1.00. It is more preferably 1.00, and further preferably 1.00. When the value of (l + m + n) / Z1 is within the above range, the low-temperature fixability becomes better.

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

The ester group-containing olefin 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 olefin copolymer. More preferably, it is 11.0% by mass to 15.0% by mass.
The ester group concentration is a value indicating how much the ester group [-C (= O) O-] bonding site in the ester group-containing olefin-based copolymer is contained in mass%. This is the value represented by the formula.
Ester group concentration (unit:%) = [(N × 44) / number average molecular weight] × 100
Here, N is the average number of ester groups per molecule of the ester group-containing olefin 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 olefin 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 as long as the storage stability of the toner can be ensured. Since it can be designed, it is preferable from the viewpoint of low-temperature fixability. Further, the ester group-containing olefin-based copolymer is easy to exhibit rubber elasticity as an elastomer, and burying of the inorganic fine particles is further reduced. Furthermore, a polymer having a higher polarity than polyethylene can be used as long as the storage stability of the toner can be ensured, the volume resistance can be further reduced, and the localization of electric charge due to triboelectric charging can be suppressed. As a result, the electrostatic adhesion between the intermediate transfer member and the toner can be reduced, which is preferable from the viewpoint of transferability.

  The acid value of the ester group-containing olefin-based 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 water adsorbed by the toner is small, which is preferable from the viewpoint of charge retention.

Further, the toner only needs to have a resin existing on the surface of the toner particles having the rubber elasticity characteristics 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 the different structure, various resin compounds conventionally known as an amorphous resin can be used in addition to the polyester resin described below.
As such an amorphous resin, for example, phenolic resin, natural resin modified phenolic resin, natural resin modified maleic resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, Epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumaroindene resins, petroleum resins and the like can be mentioned.

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 (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trivalent or higher carboxylic acids), and their anhydrides or lower anhydrides. Alkyl esters can be used.
For the polyester resin, for example, the following polyhydric alcohol monomers can be used.
Examples of the dihydric alcohol component include 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.

(In the formula, 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.)

(Where R ′ is

Indicates that
x ′ and y ′ are integers equal to or greater than 0, and the average value of x ′ + y ′ is 0 to 10. )

  Examples of the trihydric or higher alcohol component 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, and 1,3,5-trihydroxymethylbenzene No. Of these, glycerol, trimethylolpropane, and pentaerythritol are preferably used. These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination of two or more.

The following polyvalent carboxylic acid monomers can be used for the polyester resin.
Examples of the divalent carboxylic acid component 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 These lower alkyl esters are exemplified. Of these, maleic acid, fumaric acid, terephthalic acid, succinic acid, and n-dodecenylsuccinic acid are preferably used.
Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include 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 ( Examples thereof include (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, anhydrides thereof, and lower alkyl esters thereof.
Of these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or a derivative thereof, and terephthalic acid and succinic acid are particularly preferably used because they are inexpensive and easy to control the reaction. These divalent 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 a known method can be used. For example, a polyester resin can be produced by simultaneously charging the above-mentioned alcohol monomer and carboxylic acid monomer and polymerizing them through an esterification reaction or a transesterification reaction and a condensation reaction.
The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C to 290 ° C. Upon polymerization of the polyester unit, for example, a polymerization catalyst such as a titanium catalyst, a tin catalyst, zinc acetate, antimony trioxide, and germanium dioxide can be used. Of these, tin catalysts and titanium catalysts are preferred.

Further, the polyester resin may be a hybrid resin obtained by adding another resin component to the polyester resin. For example, a hybrid resin of a polyester resin and a vinyl resin may be used. As a method of obtaining a reaction product of a vinyl resin or a vinyl copolymer unit and a polyester resin, such as a hybrid resin, a monomer component capable of reacting with each of the vinyl resin or the vinyl copolymer unit and the polyester resin is included. A method in which one or both resins are polymerized in the presence of the polymer is preferred.
For example, among the monomers constituting the polyester resin component, as the monomer capable of reacting with the vinyl copolymer, for example, fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides thereof, and the like. No.
On the other hand, among the monomers constituting the vinyl resin component, those which can react with the polyester resin component include, for example, monomers having a carboxy group or a hydroxy group, acrylates or methacrylates, and the like.

The toner particles may contain a release agent. Examples of the release agent include low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point) upon heating; fatty acid amides such as oleamide, erucamide, ricinoleamide, and stearamide; Ester waxes such as stearyl stearate; plant waxes such as carnauba wax, rice wax, candelilla wax, wood wax, and jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline Mineral and petroleum waxes such as wax, Fischer-Tropsch wax and ester wax; and silicone oil.
The content of the release agent is preferably 5 parts by mass to 30 parts by mass based on the total amount of the resin components.

Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, alkyl-modified silicone oil, and fluorine-modified silicone oil. Among them, dimethyl silicone oil is preferred from the viewpoint of hot offset resistance.
When the silicone oil is dimethyl silicone oil, the silicone oil tends to exude at the time of fixing because of a large polarity difference from the ester group-containing olefin copolymer. As a result, the hot offset resistance is further improved.
The content of the silicone oil is preferably 15 parts by mass to 30 parts by mass based on the total amount of the resin components. Within such a range, the silicone oil sufficiently exudes at the time of fixing, so that hot offset resistance is further improved.
The kinematic viscosity of the silicone oil at 25 ° C. ^is preferably 300mm ² / s~1000mm 2 / s. Within this range, the silicone oil sufficiently oozes out at the time of fixing, so that the hot offset resistance is further improved.

<Colorant>
The toner particles may contain a colorant. Examples of the coloring agent include the following.
Examples of the black colorant include those toned to black using carbon black; a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the sharpness from the viewpoint of the image quality of a full-color image.
Examples of the pigment for magenta toner 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; I. Butt Red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the dye for magenta toner include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disperse Red 9; I. Solvent violet 8, 13, 14, 21, 27; I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
Examples of the pigment for cyan toner include the following. C. I. Pigment Blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat blue 6; I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of the dye for cyan toner include C.I. I. Solvent Blue 70.
Examples of the yellow toner pigment 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, C. 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.
As the dye for yellow toner, for example, C.I. I. Solvent Yellow 162.
These colorants can be used alone or as a mixture of two or more, and further in the form of a solid solution. The colorant can be selected in terms of hue angle, saturation, lightness, light fastness, OHP transparency, and dispersibility in toner.
The content of the colorant is preferably 0.1 parts by mass to 30.0 parts by mass based on the total amount of the resin components.

<Developer>
The toner can be used as a one-component developer, but it is mixed with a magnetic carrier to further improve dot reproducibility and to supply a stable image over a long period of time. It can also be used.
Examples of the magnetic carrier include iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths, alloy particles thereof, and oxide particles thereof; A generally known magnetic material such as a magnetic material such as ferrite; a magnetic material-dispersed resin carrier (a so-called resin carrier) containing a magnetic material and a binder resin holding the magnetic material in a dispersed state 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 may be 2% by mass to 15% by mass as the toner concentration in the two-component developer. It is preferably from 4% by mass to 13% by mass.

<Production method of toner>
The toner particles can be produced by any method, but are preferably 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 solution suspension method or an emulsion aggregation method. In the solution suspension method, by controlling the polarity of the resin constituting the toner particles, it is possible to control the resin so that the resin spontaneously exists on the surface of the toner particles. In the emulsion aggregation method, the surface of the toner particles can be geometrically controlled by once producing core particles in an aqueous medium as described later, and then performing an aggregation reaction with the shell particles. Therefore, it is preferable to produce toner particles by an emulsion aggregation method 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.

<Emulsion aggregation method>
With the emulsion aggregation method, an aqueous dispersion of fine particles containing a constituent material of the toner particles, which is sufficiently small with respect to the target particle size, is prepared in advance, and the fine particles become the particle size of the toner particles in an aqueous medium. This is a method in which toner particles are produced by aggregating resin particles and fusing the resin by heating.
That is, in the emulsion aggregation method, a dispersion step of preparing a fine particle dispersion liquid containing the constituent material of the toner particles, the fine particles containing the constituent material of the toner particles are aggregated, and the particle diameter is controlled until the particle diameter of the toner particles is reached. Aggregating step, fusing step for fusing the resin contained in the obtained agglomerated particles, subsequent cooling step, metal removing step for filtering the obtained toner particles to remove excess polyvalent metal ions, ion exchange The toner particles can be produced through a filtration / washing step of washing with water or the like, and a step of removing water from the washed toner particles and drying.
In the emulsion aggregation method, if necessary, a step of contacting and separating with an organic solvent, a step of treating a wet cake of toner particles obtained in a filtration and washing step with an organic solvent, or finally a drying step A step of treating the obtained toner particles with an organic solvent can be performed.

<Dispersion process>
<Resin particle dispersion>
The resin fine 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 of emulsifying a resin by adding an aqueous medium to a resin solution dissolved in an organic solvent, and without using an organic solvent. And a forced emulsification method in which the 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 this time, if the resin is a crystalline resin having a melting point, the resin may be heated to the melting point or higher to be dissolved. Subsequently, while stirring with a homogenizer or the like, an aqueous medium is slowly added to precipitate resin fine particles. Thereafter, by heating or reducing the pressure to remove the solvent, an aqueous dispersion of resin fine particles is prepared.
Here, as the organic solvent used for dissolving the ester group-containing olefin copolymer, any organic solvent that can dissolve the ester group-containing olefin copolymer can be used. It is preferable to use an organic solvent that forms a uniform phase with water, for example, from the viewpoint of suppressing generation of coarse powder.
The surfactant used at the time of the dispersion step is not particularly limited, for example, anionic surfactants such as sulfates, sulfonates, carboxylates, phosphates, and soaps A cationic surfactant such as an amine salt type or a quaternary ammonium salt type; and a nonionic surfactant such as a polyethylene glycol type, an alkylphenol ethylene oxide adduct type, or a polyhydric alcohol type. One type of surfactant may be used alone, or two or more types may be used in combination.
Examples of the basic compound used in the dispersion step include inorganic bases such as sodium hydroxide and potassium hydroxide; and organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol and diethylaminoethanol. The basic compounds may be used alone or in combination of two or more.
The dispersion particle size of the resin fine particles in the aqueous dispersion is preferably 50% particle size based on volume distribution from the viewpoint of easily obtaining toner particles having a volume average particle size of 3 μm to 10 μm which are appropriate as toner particles. (D50) is preferably from 0.05 μm to 1.0 μm, and more preferably from 0.05 μm to 0.4 μm. For measuring the 50% particle size (D50) based on the volume distribution, a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) can be used.

<Colorant fine particle dispersion>
The colorant fine particle dispersion used as needed 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 with a known mixer such as a stirrer, an emulsifier, and a disperser. As the dispersant used here, known dispersants such as a surfactant and a polymer dispersant can be used.
Both the surfactant and the polymer dispersant can be removed in the washing step described below, but from the viewpoint of washing efficiency, a surfactant is preferred.
Examples of the surfactant include anionic surfactants such as sulfates, sulfonates, phosphates, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; polyethylene. Nonionic surfactants such as glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols are included.
Among these, a nonionic surfactant or an anionic surfactant is preferable. Further, a nonionic surfactant and an anionic surfactant may be used in combination. One type of surfactant may be used alone, or two or more types may be used in combination. The concentration of the surfactant in the aqueous medium is preferably 0.5% by mass to 5% by mass.
The content of the colorant fine particles in the colorant fine particle dispersion is not particularly limited, but is preferably 1% by mass to 30% by mass based on the total mass of the colorant fine particle dispersion.
Further, from the viewpoint of the dispersibility of the colorant in the finally obtained toner, the 50% particle size (D50) based on the volume distribution is 0.5 μm or less from the viewpoint of the dispersibility of the colorant fine particles in the aqueous dispersion. It is preferable that For the same reason, the 90% particle size (D90) based on the volume distribution is preferably 2 μm or less.
The dispersion particle size of the colorant fine particles dispersed in the aqueous medium is measured by a dynamic light scattering particle size distribution analyzer (Nanotrack UPA-EX150: manufactured by Nikkiso Co., Ltd.).
Known mixers such as a stirrer, an emulsifier, and a disperser used for dispersing a colorant in an aqueous medium include, for example, an ultrasonic homogenizer, a jet mill, a pressure homogenizer, a colloid mill, a ball mill, and a sand mill. , And a paint shaker. These may be used alone or in combination.

<Release agent fine particle dispersion>
The aqueous dispersion of the release agent fine particles used as needed is, for example, adding a release agent to an aqueous medium containing a surfactant, heating to above the melting point of the release agent, and having a strong shearing ability. Disperse into particles with a homogenizer (for example, "Mare Technique W Motion" manufactured by M Technique Co., Ltd.) or a pressure discharge type dispersing machine (for example, "Gaulin Homogenizer" manufactured by Gorin Co., Ltd.), and then cool to below the melting point. Can be produced.
The dispersed particle diameter of the release agent fine particles in the aqueous dispersion is preferably such that a 50% particle diameter (d50) on a volume basis is 0.03 μm to 1.0 μm, and 0.1 μm to 0.5 μm. More preferred. More preferably, there are no coarse particles having a d50 exceeding 1.0 μm.
When the dispersion particle diameter of the release agent fine particles is within the above range, the release agent at the time of fixing becomes more eluted, the hot offset temperature can be increased, and filming on the photoconductor occurs. Can be suppressed. The dispersion particle size of the release agent fine particles dispersed in the aqueous medium can be measured by a dynamic light scattering particle size distribution size (Nanotrack: manufactured by Nikkiso Co., Ltd.).

When silicone oil is used as the release agent, it is preferable to prepare a composite fine particle dispersion in which the resin constituting the toner particles and the silicone oil are mixed. By doing so, the silicone oil content in the toner particles is increased while the amount of silicone oil on the surface of the toner particles is easily adjusted to an appropriate range, so that the transfer efficiency is further improved.
Specifically, in the step of preparing the resin fine particle dispersion, a silicone oil may be mixed with a solution obtained by dissolving the resin in an organic solvent.
In addition, the dispersion liquid of silicone oil fine particles can be prepared by known methods described below, but is not limited to these methods.
It can be prepared by mixing a silicone oil, an aqueous medium and a dispersant with a known mixer such as a stirrer, emulsifier, and disperser. As the dispersant used here, known dispersants such as a surfactant and a polymer dispersant can be used.
Although both the surfactant and the polymer dispersant can be removed in the washing step described below, a surfactant is preferred from the viewpoint of washing efficiency.
Examples of the surfactant include anionic surfactants such as sulfate, sulfonate, phosphate, and soap; cationic surfactants such as amine salt and quaternary ammonium salt; Nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols are included.
Among these, a nonionic surfactant or an anionic surfactant is preferable. Further, a nonionic surfactant and an anionic surfactant may be used in combination. One type of surfactant may be used alone, or two or more types may be used in combination. The concentration of the surfactant in the aqueous medium is preferably 0.5% by mass to 5% by mass.

The content of the silicone oil fine particles in the silicone oil fine particle dispersion is not particularly limited, but is preferably 1% by mass to 30% by mass relative to the total mass of the silicone oil fine particle dispersion.
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 from the viewpoint of easily controlling the amount of the silicone oil on the toner surface. For the same reason, the 90% particle size (D90) on a volume basis is preferably 2.0 μm or less.
The dispersed particle size of the silicone compound dispersed in the aqueous medium can be measured by a dynamic light scattering particle size distribution size (Nanotrack: manufactured by Nikkiso Co., Ltd.).
Known mixers such as a stirrer, an emulsifier, and a disperser used when dispersing silicone oil in an aqueous medium include, for example, an ultrasonic homogenizer, a jet mill, a pressure-type homogenizer, a colloid mill, a ball mill, a sand mill, And paint shakers. These may be used alone or in combination.

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

<Aggregation step>
In the aggregation step, the fine particles contained in the mixture prepared in the mixing step are aggregated to form an aggregate having a target particle diameter. At this time, by adding and mixing a coagulant, and optionally adding at least one of heating and mechanical power as needed, resin fine particles, and,
If necessary, an aggregate in which the release agent fine particles, the colorant fine particles, and the like are aggregated can be formed. In the case where the core-shell structure is formed on the toner particles, a method is preferable in which a mixture other than the fine particle dispersion of the resin forming the shell is mixed and aggregated, and then the fine particle dispersion of the resin forming the shell is added to cause the aggregation.
As the coagulant, it is preferable to use a coagulant containing a divalent or higher valent metal ion. A coagulant containing at least one metal ion selected from the group consisting of Mg, Ca, Sr, Al and Zn is more preferred.
An aggregating agent containing a divalent or higher valent metal ion has a high aggregating power and can achieve its purpose by adding a small amount thereof. These coagulants can ionically neutralize the ionic surfactant contained in the resin fine particle dispersion, the release agent dispersion, and the colorant fine particle dispersion. As a result, due to the effects of salting out and ion crosslinking, the resin fine particles, the release agent fine particles, and the colorant fine particles can be aggregated.

Examples of the coagulant 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. Further, trivalent metal salts such as iron (III) chloride, iron (III) sulfate, aluminum sulfate, and aluminum chloride can be used. In addition, inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide are included, but are not limited thereto. These may be used alone or in combination of two or more.
The coagulant may be added in any form of 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 coagulation.
The addition and mixing of the coagulant are preferably performed at a temperature lower than the glass transition temperature or the melting point of the resin contained in the mixture. Aggregation can be progressed relatively uniformly by mixing under this temperature condition. Mixing of the flocculant into the mixture can be performed using a known mixing device such as a homogenizer and a mixer.
The aggregation step is a step of forming an aggregate having a particle size substantially equal to that of the toner particles in an aqueous medium. The volume-based 50% particle size (D50) of the aggregate 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 aggregate obtained in the aggregation step under the same stirring as in the aggregation step. Examples of the aggregation terminator include 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, chelating agents, which stabilize aggregated particles by partially dissociating ionic crosslinks between acidic polar groups of surfactants and metal ions contained in the aggregating agent and forming coordination bonds with the metal ions, include chelating agents. No. Among these, a chelating agent having a greater effect of stopping aggregation is preferable.
After the dispersion state of the aggregated particles in the dispersion is stabilized by the action of the aggregation terminator, the aggregated particles can be fused by heating to a temperature higher than the glass transition temperature or the 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, for example, oxycarboxylic acids such as tartaric acid, citric acid and gluconic acid, and their sodium salts; iminodiic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA); Sodium salts thereof.
The chelating agent coordinates the metal ion of the flocculant present in the dispersion of the flocculated particles to change the environment in the dispersion from an electrostatically unstable and easily flocculated state to a statically flocculated state. The state can be changed to a state where it is stable and hardly causes further aggregation. Thereby, further aggregation of the aggregated particles in the dispersion liquid can be suppressed, and the aggregated particles can be stabilized.
It is preferable that the chelating agent is an organic metal salt having a carboxylic acid having a valence of 3 or more, since the chelating agent is effective even with a small addition amount and toner particles having a sharp particle size distribution can be obtained.
Further, the addition amount of the chelating agent 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 the stability from the aggregation state and the washing efficiency. More preferably, the amount is from 15 parts by mass to 15 parts by mass. The 50% particle size (D50) based on volume 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 fusing 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 process>
The method for producing a toner may include a metal removing step of removing a metal ion by adding a chelate compound having a chelating ability to the metal ion. The chelating compound is not particularly limited as long as it is a known water-soluble chelating agent, and the above-mentioned chelating agents can be used.

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

<Step of bringing into contact with an organic solvent and separation step>
In the step of bringing into contact with an organic solvent and the separation step, the toner particles obtained in the washing step can be separated by contact with an organic solvent, if necessary. By this step, the low-molecular-weight silicone compound having a high affinity for the organic solvent is washed, and a thin film of the silicone compound having a sharp molecular weight distribution can be formed on the surface of the toner particles.
The organic solvent used in the step is different from a conventional solvent for cleaning a release agent, and it is preferable that the organic solvent has a lower affinity than the silicone compound by a certain value or more. If the affinity is too high, the silicone compound, which is a release agent, is too much extracted from the toner particles, and the fixing / separating property is reduced. 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 parts by mass to 10 parts by mass with respect to 100 parts by mass of the organic solvent. When the content is within the above range, the low molecular weight silicone compound near the surface of the toner particles is easily removed.
The processing time of the contact step between the toner particles and the organic solvent is preferably 1 minute to 60 minutes.
In the step of contacting the toner particles with 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 a stirring blade, or may be performed by a homogenizer or an ultrasonic disperser. However, from the viewpoint of uniformly treating the toner particles, the treatment is preferably performed with stirring using a homogenizer, an ultrasonic disperser, or the like.
The step of separating the toner particles from 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 method of separation 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 contact step and the separation step between the toner particles and the organic solvent may be performed by repeating the contact and separation steps a plurality of times. In particular, when a mixture of a toner wet cake and an organic solvent is treated, the efficiency of removal of the silicone compound may be reduced due to the effect of water present in the toner wet cake.

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

<External addition process>
In the external addition step, inorganic 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 inorganic fine particles having a rectangular parallelepiped particle shape may be externally added.
Specifically, silica, alumina, titania, inorganic fine particles such as calcium carbonate, resin fine particles such as vinyl resin, polyester resin, silicone resin, and inorganic fine particles having a rectangular parallelepiped particle shape, in a dry state It is preferable to add by applying a shearing force.

  Methods for measuring various physical properties of the toner and the raw materials will be described below.

<Method of 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-fine indentation hardness tester “ENT1100a” (manufactured by Elionix), which is one of the ultra-micro hardness measuring devices.
The resin existing on the surface of the toner particles is sprayed on the stage, and while confirming with an optical microscope, the stage is moved so that one particle of the resin existing on the surface of the toner particles is at the center, and positional information is recorded and measured. I do.
The measurement conditions are as follows.
Load: 50μN
Temperature: 25 ° C
Number of divisions: 1000 Step interval: 50 msec
Indenter: 50 μm plane indenter FIG. 1 shows the measurement results of the resin used in Example 1. The displacement h is a displacement when a test load of 50 μN is applied. The plastic deformation rate H is calculated by using the following formula, when a test load of 50 μN is applied, and when the test load is returned to 0 μN, the displacement x that could not be returned was read.
Plastic deformation rate H = {displacement x / displacement h} × 100
In the case of measuring from the toner, after the resin present on the surface of the toner particles is separated from the toner by a method described later, the displacement h and the plastic deformation rate H are obtained using the resin.

<Method of measuring SP value (SP1 and SP2)>
The SP values (SP1 and SP2, respectively) of the resin and the surface treatment agent of the inorganic fine particles present on the surface of the toner particles are as follows. After identifying the chemical structure by NMR and calculating the molar ratio, the Fedors equation is calculated as follows. Determine using Here, the values of Δei and Δvi are calculated based on the evaporation energy and the molar volume of the atoms and atomic groups according to Table 3-9 described on pages 54 to 57 of “Basic Science of Coating” (1986 (Maki Shoten)). 25 ° C.).
Formula: δi = [Ev / V] ^1/2 = [Δei / Δvi] ^1/2
Ev: Evaporation energy V: Molar volume Δei: Evaporation energy of atom or atomic group of i component Δvi: Molar volume of atom or atomic group of i component The monomer structure and the molar ratio of the ester group-containing olefin copolymer are ¹ H Determined by NMR. Under the following conditions, the unit ratio of each unit is calculated by measuring the integral ratio of hydrogen in the side chain of the monomer structure of the ester group-containing olefin copolymer, and comparing them.
Apparatus: JNM-ECZR series FT NMR (manufactured by JEOL JEOL Ltd.)
Solvent: 5 mL of heavy acetone (tetramethylsilane is included as an internal standard with a chemical shift of 0.00 ppm)
Sample: 5mg
Repetition time: 2.7 seconds Integration frequency: 16 For example, the calculation of the unit ratio of the ester group-containing olefin copolymer 1 (ethylene-vinyl acetate copolymer) used in Example 1 is 1.14 ppm to 1 peak of .36ppm corresponds to _CH 2 -CH ₂ ethylene units, since the peak around 2.04ppm corresponds to CH ₃ of vinyl acetate units, carried out by calculating the ratio of integral values of those peaks.
From the obtained molar ratio, the SP value is calculated by using the Fedors equation.

<Method of measuring surface potential B>
The surface potential B is derived by performing the following rub test using inorganic fine particles and a resin present on the surface of the toner particles.
First, a resin piece is prepared using a resin existing on the surface of the toner particles. The resin piece is produced by applying pressure on a hot plate heated to a temperature higher than the melting point of the resin.
Next, the surface of the produced resin piece is neutralized by a neutralizer. The resin piece is neutralized by irradiating the resin piece with X-rays (tube voltage 15 kV, irradiation angle 130 °) for 30 seconds or more by an X-ray generator (Photoionizer manufactured by Hamamatsu Photonics). It is confirmed by a surface electrometer (model 347 manufactured by Trek Japan) that the electric potential of the resin piece is −50 V to +50 V to confirm that no electric potential remains on the resin piece. Here, the distance between the surface electrometer 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 similarly prepared and rubbed 30 times.
Here, the surface potential of the resin piece measured in a state where the inorganic fine particles adhere to the resin piece is defined as a surface potential D.
The surface potential measured using the resin piece from which the inorganic fine particles have been removed by air blowing so as not to generate triboelectric charging is defined as a surface potential E.
By calculating the difference between the surface potential D and the surface potential E, the surface potential B is calculated.

That is, the surface potential B can be obtained by the following equation.
Surface potential B = (Surface potential D of the resin piece measured in a state where the resin particles of the resin present on the surface of the toner particles are rubbed with the inorganic fine particles and then the inorganic fine particles are attached to the resin particles) − (Surface potential E measured using a resin piece obtained by rubbing a resin piece of resin present on the surface of the toner particles with the inorganic fine particles and then removing the inorganic fine particles by air blowing)
In the case of measurement from the toner, the resin and the inorganic fine particles present on the surface of the toner particles are separated from the toner by a method described later, and then the surface potential B can be obtained using the resin and the inorganic fine particles.

<Method of Measuring Shape and Number Average Particle Size (D1) of Primary Particles of Inorganic Fine Particles>
The number average particle diameter of the primary particles of the inorganic fine particles is determined by observing the inorganic fine particles present on the surface of the toner particles with a scanning electron microscope. As the scanning electron microscope, Hitachi Ultra High Resolution Field Emission Scanning Electron Microscope S-4800 (manufactured by Hitachi, Ltd.) is used. The image shooting conditions of S-4800 are as follows. Note that element analysis is performed by an energy dispersive X-ray analyzer (manufactured by EDAX) in advance, and measurement is performed after confirming that each particle is silica fine particles or titanium oxide fine particles.

(1) Sample preparation A conductive paste is thinly applied to a sample stage (aluminum sample stage 15 mm x 6 mm), and toner is sprayed on the conductive paste. Further, the air is blown off to remove excess toner from the sample stage and sufficiently dry. The sample stage is set on the sample holder, and the height of the sample stage is adjusted to 36 mm by the sample height gauge.
(2) Setting of S-4800 Observation Conditions The calculation of the number average particle diameter of the primary particles of the inorganic fine particles is performed using the image obtained by the backscattered electron image observation of S-4800. Since the reflected electron image has less charge-up of the inorganic fine particles than the secondary electron image, the particle diameter of the inorganic fine particles can be measured with high accuracy.
Inject the liquid nitrogen into the anti-contamination trap attached to the housing of S-4800 until it overflows, and leave it for 30 minutes. The “PCSTEM” of S-4800 is started, and flushing (cleaning of the FE chip as an electron source) is performed. Click the acceleration voltage display area on 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 flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel and move the sample holder to the observation position. Click the acceleration voltage display section 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], set the SE detector to [Upper (U)] and [+ BSE], and select [+ BSE] in the selection box to the right of [+ BSE]. L. A. 100] to set a mode for observing with a backscattered electron image. Similarly, in the [Basic] tab of the operation panel, the probe current of the electron optical system condition block is set to [Normal], the focus mode is set to [UHR], and the WD is set 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 the inside of the magnification display section of the control panel to set the magnification to 100000 (100k) times. The focus knob [COARSE] on the operation panel is rotated, and the aperture alignment is adjusted when the focus is reached to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. By rotating the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel, the displayed beam is moved to the center of the concentric circle. Next, "Aperture" is selected, and the STIGMA / ALIGNMENT knobs (X, Y) are turned one by one to stop the movement of the image or adjust the image to the minimum movement. Close the aperture dialog and focus with auto focus. This operation is repeated twice more, the focus is adjusted, and the particle size is measured. The particle diameter of at least 300 inorganic fine particles on the surface of the toner particles is measured to determine the number average particle diameter (D1).

<Method for measuring content of ester group-containing olefin copolymer>
The content of the ester group-containing olefin copolymer present on the surface of the toner particles is determined by utilizing the difference in the easiness of dyeing the amorphous resin and the ester group-containing olefin copolymer with ruthenium tetroxide. It is calculated by observing the cross section of the particles.
First, as a specific method for measuring the cross-sectional morphology of the toner particles, first, 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 provided with diamond teeth to produce a flaky sample.
After the sample is stained 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 above observation method, the amorphous part of the toner particles is strongly dyed by ruthenium tetroxide. As a result, the portion mainly containing the amorphous resin is dyed, and the portion mainly containing the ester group-containing olefin copolymer is not dyed, and can be observed as a contrast. The observation magnification is 20000 times. The surface of the toner particles refers to a region from 0 nm to 100 nm from the outer surface of the toner particles toward the center (the middle point of the long axis) in the cross section observation of the toner using a TEM. The content is calculated from the area ratio of the dyed part to the non-dyed part and the specific gravity of the amorphous resin and the ester group-containing olefin copolymer within the above range.

<Method for measuring ester group concentration of ester group-containing olefin copolymer>
The ester group concentration of the ester group-containing olefin copolymer is determined by ¹ H NMR. Under the following conditions, the unit ratio of each unit is calculated by measuring the integral ratio of hydrogen in the side chain of the monomer structure of the ester group-containing olefin copolymer, and comparing them. The ester group concentration is calculated by introducing the obtained unit ratio into the following equation.
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 olefin 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 of heavy acetone (tetramethylsilane is included as an internal standard with a chemical shift of 0.00 ppm)
Sample: 5mg
Repetition time: 2.7 seconds Integration frequency: 16 For example, the calculation of the unit ratio of the ester group-containing olefin copolymer 1 (ethylene-vinyl acetate copolymer) used in Example 1 is 1.14 ppm to 1 peak of .36ppm corresponds to _CH 2 -CH ₂ ethylene units, since the peak around 2.04ppm corresponds to CH ₃ of vinyl acetate units, carried out by calculating the ratio of integral values of those peaks.

(When measuring from toner)
The above measurement is carried out after separating the resin present on the surface of the toner particles and the inorganic fine particles having a rectangular parallelepiped particle shape from the toner by utilizing the difference in solubility in the solvent.
In the cross-sectional observation of the toner particles, the resin existing on the surface of the toner particles and the resin existing on the surface of the toner particles from the toner in which the resin existing on the surface of the toner particles is not the same as the resin existing inside the toner particles, The separation of the inorganic fine particles having the following is performed by the following procedure.
First separation: The toner is dissolved in MEK at 23 ° C., and the soluble component (amorphous resin) and the insoluble component (resin, releasing agent, colorant, inorganic fine particles present on the surface of the toner particles) are separated.
Second separation: Insoluble matter (resin, release agent, colorant, inorganic fine particles present on the surface of toner particles) obtained in the first separation is dissolved in toluene at 50 ° C. The resin existing on the surface) and the 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).

In the cross-sectional observation 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. Is performed in the following procedure.
The toner is dissolved in MEK at 23 ° C., and the soluble component (resin) and the insoluble component (release agent, colorant, inorganic fine particles) are separated.
The above measurement is performed using the obtained soluble component (resin).

<Method of Measuring Weight Average Particle Diameter (D4) of Toner>
The weight-average particle diameter (D4) of the toner can be measured with a precision particle size distribution analyzer “Coulter Counter Multisizer” using a pore electric resistance method equipped with an aperture tube of 100 μm.
3 "(registered trademark, manufactured by Beckman Coulter) and dedicated software" Beckman Coulter Multisizer 3 Version 3.51 "(manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data. The measurement is performed with 25,000 effective measurement channels, and the measured data is analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, a solution prepared by dissolving a special grade sodium chloride in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter) can be used.
Before performing measurement and analysis, the dedicated software is set as follows.
In the “Change standard measurement method (SOM) screen” of the dedicated software, the total count in the control mode is set to 50,000 particles, the number of measurements is set to 1, and the Kd value is set to “standard particles 10.0 μm” (Beckman Coulter, Inc.). Set the value obtained using By pressing the threshold / noise level measurement button, the threshold and the noise level are automatically set. Also, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check mark is placed in the flash of the aperture tube after the measurement.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measuring method is as follows.
(1) About 200 mL of the aqueous electrolytic solution is placed in a glass 250 mL round bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 revolutions / second. Then, the dirt and air bubbles in the aperture tube are removed by the “flash aperture tube” function of the dedicated software.
(2) About 30 mL of the electrolytic aqueous solution is placed in a 100 mL flat-bottom beaker made of glass, into which “Contaminone N” (a precise measurement of pH 7 comprising a nonionic surfactant, an anionic surfactant, and 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 with a container (manufactured by Wako Pure Chemical Industries, Ltd.) 3 times by mass with ion-exchanged water is added.
(3) Two oscillators having an oscillation frequency of 50 kHz are built in a state shifted by 180 degrees, and are placed in the water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios) having an electric output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 mL of the contaminone 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 aqueous electrolytic solution in the beaker is maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is 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 processing is continued for another 60 seconds. The ultrasonic dispersion is appropriately adjusted so that the water temperature in the water tank is 10 ° C to 40 ° C.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolytic aqueous solution of (5) in which the toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to about 5%. . Then, measurement is performed until the number of particles to be measured reaches 50,000.
(7) Analyze the measured data with the dedicated software attached to the device, and calculate the weight average particle size (D4). The “average diameter” on the “analysis / volume statistical value (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<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 the measurement and analysis conditions during the calibration operation.
The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is sent to a flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow forms a flat flow between the sheath liquids. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, so that the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is captured in a focused state.
The particle image is captured by a CCD camera, and the captured image is processed at an image processing resolution of 512 × 512 pixels (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted. Are measured.
Next, using the area S and the perimeter L, the equivalent circle diameter and circularity are determined. The circle equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the circle equivalent diameter by the circumference of the particle projection image. And is calculated by the following equation.
Circularity C = 2 × (π × S) ^1/2 / L
The circularity is 1.000 when the particle image is circular, and the circularity becomes smaller as the degree of irregularities on the outer periphery of the particle image increases. After calculating the circularity of each particle, the range of the circularity of 0.200 to 1.000 is divided into 800, and the arithmetic mean of the obtained circularities is calculated, and the value is defined as the average circularity.

The specific measuring method is as follows.
First, about 20 mL of ion-exchanged water from which impurity solids and the like have been removed in advance is placed in a glass container. As a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument having a pH of 7 comprising a nonionic surfactant, an anionic surfactant and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) ) Was diluted about 3 times by mass with ion-exchanged water, and about 0.2 mL of a diluent was added.
Further, about 0.02 g of a measurement sample is added, and a dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. At this time, the dispersion is appropriately cooled so that the temperature of the dispersion becomes 10 ° C to 40 ° C. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervocreer)) having an oscillation frequency of 50 kHz and an electric output of 150 W was used. Exchange water is added, and about 2 mL of the contaminone N is added to the water tank.
For the measurement, the flow type particle image analyzer equipped with a standard objective lens (× 10) is used, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and 3,000 toner particles are measured in the HPF measurement mode in the total count mode.
Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is set to a circle equivalent diameter of 1.98 μm to 39.96 μm, and the average circularity of the toner is obtained.
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) with ion-exchanged water before the start of 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 Resin Fine Particles, Release Agent Fine Particles, and Colorant Fine Particles>
A dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso) is used to measure the 50% particle size (D50) based on the volume distribution of the resin fine particles, the release agent fine particles, and the colorant fine particles. In order to prevent aggregation of the measurement sample (resin fine particles), a dispersion in which the measurement sample is dispersed in an aqueous solution containing Family Fresh (manufactured by Kao Corporation) is added and stirred. Thereafter, this is injected into the above-mentioned device, and measurement is performed twice, and the average value is obtained.
As measurement conditions, the measurement time is 30 seconds, the refractive index of the sample particles is 1.49, the dispersion medium is water, and the refractive index of the dispersion medium 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. .

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, all “parts” of each material in the examples and comparative examples are based on mass.

<Example of producing ester group-containing olefin copolymer 1 (R ¹ = H, R ² = H, R ³ = CH ₃ )>
-75.2 parts of ethylene (90.3 mol% based on the total number of moles)
・ 24.8 parts of vinyl acetate (9.7 mol% based on the total number of moles)
-Isobutyraldehyde (chain transfer agent) 4.2 parts-Di-t-butyl peroxide (radical generating catalyst) 0.0025 parts The above materials are weighed and sent to a tubular reactor using a high-pressure pump, and the reaction pressure is increased. Ethylene and vinyl acetate were copolymerized under the polymerization conditions of 240 MPa and a reaction peak temperature of 250 ° C. to obtain an ester group-containing olefin copolymer 1. The obtained 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 min, and an acid value (Av) of 0 mgKOH. / G.

<Examples of production of ester group-containing olefin 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 the number of parts by mass were changed as shown in Table 1, and the ester group-containing olefin copolymers 2 to 6 were produced. Obtained.

<Production Example of Amorphous Resin 1>
・ Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
76.3 parts (50.0 mol% based on the total number of moles)
・ 16.1 parts of terephthalic acid (30.0 mol% based on the total number of moles)
7.6 parts of succinic acid (20.0 mol% based on the total number of moles)
-Titanium tetrabutoxide (esterification catalyst) 0.5 parts The above materials were weighed in a cooling tube, a stirrer, a nitrogen introducing tube, and a reaction vessel equipped with a thermocouple.
Next, after the inside of the reaction tank was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was performed for 4 hours while stirring at a temperature of 200 ° C.
0.1 parts of tert-butyl catechol (polymerization inhibitor) Then, after confirming that the softening point measured according to ASTM D36-86 has reached a desired temperature, the above materials are added to lower the temperature to stop the reaction. Thus, 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 Particle 1>
After meta-titanic acid obtained by the sulfuric acid method was subjected to deiron bleaching treatment, an aqueous sodium hydroxide solution was added to adjust the pH to 9.0, desulfurization treatment was performed, and then neutralized to pH 5.8 with hydrochloric acid, followed by filtration and water washing. After a slurry of 1.5 mol / L as TiO ₂ Water was added to the washed cake was deflocculated treated with pH1.5 with hydrochloric acid.
The metatitanic acid that had been desulfurized and peptized was collected as TiO ₂ and charged into a 3 L reaction vessel. The該解glue metatitanic acid slurry, strontium chloride aqueous solution, after addition to a 1.15 SrO / TiO ₂ molar ratio was adjusted to TiO ₂ concentration 0.8 mol / L. Next, the mixture was heated to 90 ° C. while stirring and mixing, and 444 mL of a 10 mol / L aqueous sodium hydroxide solution was added over 50 minutes while performing microbubbling of nitrogen gas at 600 ml / min, and then microbubbling of nitrogen gas was performed. And stirring at 95 ° C. for 1 hour.
Thereafter, the reaction slurry was stirred while flowing cooling water at 10 ° C. into the jacket of the reaction vessel, rapidly cooled to 15 ° C. at a cooling rate of 10 ° C./min, hydrochloric acid was added until the pH reached 2.0, and stirring was continued for 1 hour. Was. After the obtained precipitate was washed by decantation, 6 mol / L hydrochloric acid was added to adjust the pH to 2.0, and 8.0 mass% of n-octylethoxysilane with respect to the solid content was added, followed by stirring for 18 hours. Was. The mixture was neutralized with a 4 mol / L aqueous sodium hydroxide solution, stirred for 2 hours, filtered and separated, and dried in the air at 120 ° C. for 8 hours to obtain inorganic fine particles 1. Observation of the shape by electron microscopy revealed a cubic shape, and the average primary particle diameter calculated on a number basis was 50 nm. Table 2 shows the physical properties.

<Production example of inorganic fine particles 2 to 10>
In the same manufacturing method as that of the inorganic fine particles 1, inorganic fine particles 2 to 9 were produced by changing the material type of the base material, the addition time of the 10 mol / L aqueous sodium hydroxide solution, the cooling rate, and the surface treatment agent type. Table 2 shows the physical properties.

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) 300 parts Ester group-containing olefin copolymer 1 100 parts The above materials were weighed and 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. Then, the above-mentioned toluene solution and the aqueous solution were mixed, and an ultra-high-speed stirring device 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 type dispersing machine Nanomizer (manufactured by Yoshida Kikai Kogyo). Thereafter, the toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water. The aqueous dispersion of the ester group-containing olefin copolymer fine particles 1 having a concentration of 20% (the ester group-containing olefin copolymer fine particles 1 was dispersed). Liquid).
The 50% particle size (D50) based on the volume distribution of the ester group-containing olefin-based copolymer fine particles 1 was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.). It was 40 μm. Table 3 shows the physical properties.

<Production example of dispersion liquid of ester group-containing olefin-based copolymer fine particles 2 to 5>
Emulsion was performed in the same manner as in the production example of the dispersion liquid of the ester group-containing olefin copolymer fine particles 1 except that each ester group-containing olefin copolymer was changed as shown in Table 3, and the ester group-containing olefin copolymer was obtained. Dispersions of 2 to 5 copolymer fine particles were obtained. Table 3 shows the physical properties of the dispersion liquids of the ester group-containing olefin copolymer fine particles 2 to 5.

<Production Example of Amorphous Resin Fine Particle 1 Dispersion>
-300 parts of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.)-100 parts of amorphous resin 1-0.5 part of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 0.5 parts of the above materials were weighed, mixed and dissolved.
Next, 20.0 parts of 1 mol / L aqueous ammonia was added, and the ultrahigh-speed stirring device T.A. 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 a 20% aqueous dispersion of the amorphous resin fine particles 1 (amorphous resin fine particle 1 dispersion).
The 50% particle size (D50) based on the volume distribution of the amorphous resin 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 Shin-Etsu Chemical: KF96-500CS kinematic viscosity 500 mm ² / s)
・ 5 parts of anionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) ・ 395 parts of ion-exchanged water The above materials are weighed, mixed and dissolved, and about 1% using a high pressure impact disperser Nanomizer (Yoshida Kikai Kogyo). After time dispersion, an aqueous dispersion (silicone oil fine particle dispersion) having a concentration of 20% of silicone oil fine particles obtained by dispersing silicone oil was obtained.
The 50% particle size (D50) based on the volume distribution of the silicone oil fine particles was measured using a dynamic light scattering type 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>
・ 100 parts of aliphatic hydrocarbon compound HNP-51 (manufactured by Nippon Seiro) ・ 5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) ・ 395 parts of ion-exchanged water The above materials are weighed and mixed with a stirrer. After being charged into the container, the mixture was heated to 90 ° C. and circulated through Clearmix W Motion (manufactured by M Technique) to perform a dispersion treatment for 60 minutes. The conditions of the distributed processing were as follows.
・ Rotor outer diameter 3cm
・ Clearance 0.3mm
・ Rotor rotation speed 19000r / min
・ Screen rotation speed 19000r / min
After the dispersion treatment, the system is cooled 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 (aliphatic hydrocarbon compound fine particle dispersion) was obtained.
The 50% particle size (D50) based on the volume distribution of the aliphatic hydrocarbon compound fine particles was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm. .

<Manufacture of colorant fine particle dispersion>
・ Colorant 50.0 parts (Cyan pigment manufactured by Dainichi Seika: Pigment Blue 15: 3)
・ 7.5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) ・ 442.5 parts of ion-exchanged water The above materials are weighed, mixed, and dissolved. The mixture was dispersed for about 1 hour to obtain an aqueous dispersion (colorant fine particle dispersion) having a colorant fine particle concentration of 10%, in which the colorant was dispersed.
The 50% particle size (D50) based on the volume distribution of the colorant fine particles was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.

<Production Example of Toner 1>
-480 parts of an ester group-containing olefin copolymer fine particle 1 dispersion liquid-125 parts of a silicone oil fine particle dispersion liquid-80 parts of a colorant fine particle dispersion liquid-80 parts-ion-exchanged water 160 parts After mixing, 60 parts of a 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). Thereafter, the mixture was heated to 73 ° C. in a heating water bath using a stirring blade while appropriately adjusting the rotation speed 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 checked using a Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. I confirmed that it was done.
After adding 330 parts of a 5% aqueous solution of sodium ethylenediaminetetraacetate to the dispersion of the aggregated particles, the mixture was heated to 98 ° C. while stirring was continued. Then, the particles were kept at 98 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, the temperature was cooled to 50 ° C. and maintained for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
Thereafter, as a step of removing divalent metal ions derived from the coagulant, the substrate was washed with a 5% aqueous solution of sodium ethylenediaminetetraacetate while maintaining the temperature at 50 ° C.
Thereafter, the mixture was cooled to 25 ° C., filtered, and solid-liquid separated, and then washed with ion-exchanged water. After the completion of the washing, the toner particles were dried using a vacuum dryer to obtain toner particles 1 having a weight average particle diameter (D4) of about 6.07 μm. The resin present on the surface of the toner particles 1 was the ester group-containing olefin copolymer 1.
-100 parts of toner particles 1-3 parts of inorganic fine particles 1-1 part of small-particle silica particles surface-treated with hexamethyldisilazane having an average particle diameter of 20 nm 1 part Henschel mixer type FM-10C (manufactured by Mitsui Miike Kakoki Co., Ltd.) The toner 1 was obtained by mixing at a rotation speed of 30 s ^-1 and a rotation time of 10 min.
Toner 1 had a weight average particle size (D4) of 6.07 μm and an average circularity of 0.975. Table 4 shows the physical properties.

<Production 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 dispersion liquid of the ester group-containing olefin-based copolymer fine particles 1 and the inorganic fine particles 1 were changed as shown in Table 4. Resins present on the surfaces of the toner particles 2 to 12 were ester group-containing olefin copolymers shown in the column of resin type in Table 4, respectively. Table 4 shows the physical properties of Toners 2 to 12.

<Production Example of Toner 13>
480 parts of amorphous resin fine particle 1 dispersion (resin 1 forming core)
-150 parts of an aliphatic hydrocarbon compound fine particle dispersion liquid-80 parts of a colorant fine particle dispersion liquid-160 parts of ion-exchanged water 160 parts of the above materials were charged into a round stainless steel flask, mixed, and then 60 parts of a 10% aqueous magnesium sulfate solution was added. Was added. Subsequently, the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). Thereafter, the mixture was heated to 73 ° C. in a heating water bath using a stirring blade while appropriately adjusting the rotation speed 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 checked using a Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. Then, the material of the resin 2 forming the following shell was charged over 3 minutes.
20 parts of dispersion liquid of ester group-containing olefin-based copolymer fine particles 1 were charged, and after maintaining at 73 ° C. for 10 minutes, the volume average particle diameter of the formed aggregated particles was measured using Coulter Multisizer III to obtain a weight average particle diameter. It was confirmed that aggregated particles having (D4) of about 6.07 μm were formed.
After adding 330 parts of a 5% aqueous solution of sodium ethylenediaminetetraacetate to the dispersion of the aggregated particles, the mixture was heated to 98 ° C. while stirring was continued. Then, the particles were kept at 98 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, the temperature was cooled to 50 ° C. and maintained for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
Thereafter, as a step of removing divalent metal ions derived from the coagulant, the substrate was washed with a 5% aqueous solution of sodium ethylenediaminetetraacetate while maintaining the temperature at 50 ° C.
Thereafter, the mixture was cooled to 25 ° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After the completion of the washing, the toner particles 13 having a weight average particle diameter (D4) of about 6.07 μm were obtained by drying using a vacuum dryer. The resin present on the surface of the toner particles 13 was the ester group-containing olefin copolymer 1.
・ 100 parts of toner particles 13 ・ 3 parts of inorganic fine particles 1 ・ 1 part of small-particle silica fine particles surface-treated with hexamethyldisilazane having an average particle diameter of 20 nm The toner 13 was obtained by mixing at a rotation speed of 30 s ^-1 and a rotation time of 10 min.
The weight average particle diameter (D4) of the 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 the amount of the dispersion liquid of the ester group-containing olefin-based copolymer fine particles 1 was changed to 50 parts. The resin existing on the surface of the toner particles 14 was the ester group-containing olefin copolymer 1.

<Production Example of Toner 15>
A toner 15 was obtained in the same manner as in the production example of the toner 1 except that the inorganic fine particles 1 were changed to the inorganic fine particles 10. The resin present on the surface of the toner particles 15 was the ester group-containing olefin copolymer 1.

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

<Production Example of Toner 17>
-500 parts of amorphous resin fine particle 1 dispersion liquid-150 parts of aliphatic hydrocarbon compound fine particle dispersion liquid-80 parts of colorant fine particle dispersion liquid-160 parts of ion-exchanged water 160 parts The above materials are put into a round stainless steel flask and mixed. After that, 60 parts of a 10% aqueous solution of magnesium sulfate was added. Subsequently, the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). Thereafter, the mixture was heated to 73 ° C. in a heating water bath using a stirring blade while appropriately adjusting the rotation speed 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 checked using a Coulter Multisizer III, and the 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% aqueous solution of sodium ethylenediaminetetraacetate to the dispersion of the aggregated particles, the mixture was heated to 98 ° C. while stirring was continued. Then, the particles were kept at 98 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, as a step of removing divalent metal ions derived from the coagulant, the substrate was washed with a 5% aqueous solution of sodium ethylenediaminetetraacetate while maintaining the temperature at 50 ° C.
Thereafter, the mixture was cooled to 25 ° C., filtered, and solid-liquid separated, and then washed with ion-exchanged water. After completion of the washing, the resultant was dried using a vacuum dryer to obtain toner particles 17 having a weight average particle diameter (D4) of about 6.07 μm. The resin present on the surface of the toner particles 17 was the amorphous resin 1.
-100 parts of toner particles 17-3 parts of inorganic fine particles-1 part of fine silica particles having a surface treatment with hexamethyldisilazane having an average particle diameter of 20 nm 1 part Henschel mixer type FM-10C (manufactured by Mitsui Miike Koki 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 diameter (D4) of the 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 a 10% aqueous solution of magnesium sulfate was added. Subsequently, the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). Thereafter, the mixture was heated to 73 ° C. in a heating water bath using a stirring blade while appropriately adjusting the rotation speed 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 checked using a Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. I confirmed that it was done.
After adding 330 parts of a 5% aqueous solution of sodium ethylenediaminetetraacetate to the dispersion of the aggregated particles, the mixture was heated to 98 ° C. while stirring was continued. Then, the particles were kept at 98 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, the temperature was cooled to 50 ° C. and maintained for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
Thereafter, as a step of removing divalent metal ions derived from the coagulant, the substrate was washed with a 5% aqueous solution of sodium ethylenediaminetetraacetate while maintaining the temperature at 50 ° C.
Thereafter, the mixture was cooled to 25 ° C., filtered, and solid-liquid separated, and then washed with ion-exchanged water. After the completion of the washing, the toner particles 18 having a weight average particle diameter (D4) of about 6.07 μm were obtained by drying using a vacuum dryer. The resin present on the surface of the toner particles 18 was the ester group-containing olefin copolymer 5.
• 100 parts of toner particles 18 • 3 parts of inorganic fine particles 1 • 1 part of small-particle silica fine particles surface-treated with hexamethyldisilazane having an average particle size of 20 nm 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 diameter (D4) of the 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 exchange water 160 parts Each material was put into a round stainless steel flask, mixed, and then 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). Thereafter, the mixture was heated to 73 ° C. in a heating water bath using a stirring blade while appropriately adjusting the rotation speed 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 checked using a Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. I confirmed that it was done.
After adding 330 parts of a 5% aqueous solution of sodium ethylenediaminetetraacetate to the dispersion of the aggregated particles, the mixture was heated to 98 ° C. while stirring was continued. Then, the particles were kept at 98 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, the temperature was cooled to 50 ° C. and maintained for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
Thereafter, as a step of removing divalent metal ions derived from the coagulant, the substrate was washed with a 5% aqueous solution of sodium ethylenediaminetetraacetate while maintaining the temperature at 50 ° C.
Thereafter, the mixture was cooled to 25 ° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After completion of the washing, the toner particles 19 were dried using a vacuum dryer to obtain toner particles 19 having a weight average particle diameter (D4) of about 6.07 μm. The amorphous resin 1 and the ester group-containing olefin copolymer fine particles 1 were mixed on the surface of the toner particles 19.
・ 100 parts of toner particles 19 ・ 3 parts of inorganic fine particles 1 ・ 1 part of small-particle silica fine particles surface-treated with hexamethyldisilazane having an average particle diameter of 20 nm 1 part Henschel mixer FM-10C type (manufactured by Mitsui Miike Koki Co., Ltd.) The toner was obtained by mixing at a rotation speed of 30 s ^-1 and a rotation time of 10 min.
The weight average particle diameter (D4) of the toner 19 was 6.07 μm, and the average circularity was 0.975.

<Production Example of Toner 20>
-480 parts of an ester group-containing olefin copolymer fine particle 1 dispersion liquid-125 parts of a silicone oil fine particle dispersion liquid-80 parts of a colorant fine particle dispersion liquid-80 parts-ion-exchanged water 160 parts After mixing, 60 parts of a 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). Thereafter, the mixture was heated to 73 ° C. in a heating water bath using a stirring blade while appropriately adjusting the rotation speed 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 checked using a Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. I confirmed that it was done.
After adding 330 parts of a 5% aqueous solution of sodium ethylenediaminetetraacetate to the dispersion of the aggregated particles, the mixture was heated to 98 ° C. while stirring was continued. Then, the particles were kept at 98 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, the temperature was cooled to 50 ° C. and maintained for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
Thereafter, as a step of removing divalent metal ions derived from the coagulant, the substrate was washed with a 5% aqueous solution of sodium ethylenediaminetetraacetate while maintaining the temperature at 50 ° C.
Thereafter, the mixture was cooled to 25 ° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After the washing, the toner particles 20 having a weight average particle diameter (D4) of about 6.07 μm were obtained by drying using a vacuum dryer. The resin present on the surface of the toner particles 20 was the ester group-containing olefin copolymer 1.
100 parts of toner particles 20 Inorganic fine particles 11 (large-diameter spherical silica fine particles surface-treated with hexamethyldisilazane having an average particle diameter of 100 nm) 3 parts Small particle diameter treated with hexamethyldisilazane having an average particle diameter of 20 nm Silica fine particles 1 part The above materials were mixed with a Henschel mixer type FM-10C (manufactured by Mitsui Miike Kakoki Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min to obtain a toner 20.
The weight average particle diameter (D4) of the toner 20 was 6.07 μm, and the average circularity was 0.975.

<Production Example of Toner 21>
-480 parts of an ester group-containing olefin copolymer fine particle 1 dispersion liquid-125 parts of a silicone oil fine particle dispersion liquid-80 parts of a colorant fine particle dispersion liquid-80 parts-ion-exchanged water 160 parts After mixing, 60 parts of a 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). Thereafter, the mixture was heated to 73 ° C. in a heating water bath using a stirring blade while appropriately adjusting the rotation speed 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 checked using a Coulter Multisizer III, and aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed. I confirmed that it was done.
After adding 330 parts of a 5% aqueous solution of sodium ethylenediaminetetraacetate to the dispersion of the aggregated particles, the mixture was heated to 98 ° C. while stirring was continued. Then, the particles were kept at 98 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, the temperature was cooled to 50 ° C. and maintained for 3 hours to promote crystallization of the ethylene-vinyl acetate copolymer.
Thereafter, as a step of removing divalent metal ions derived from the coagulant, while maintaining at 50 ° C., 5
And washed with a 5% aqueous solution of sodium ethylenediaminetetraacetate.
Thereafter, the mixture was cooled to 25 ° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After the washing, the toner particles 21 having a weight average particle diameter (D4) of about 6.07 μm were obtained by drying using a vacuum dryer. The resin present on the surface of the toner particles 21 was the ester group-containing olefin copolymer 1.
100 parts of toner particles 21 inorganic fine particles 12 (needle-shaped titanium oxide fine particles surface-treated with hexamethyldisilazane having an average particle diameter of 50 nm) 3 parts small-particle silica surface-treated with hexamethyldisilazane having an average particle diameter of 20 nm Fine Particles 1 part Each of the above materials was mixed with a Henschel mixer type FM-10C (manufactured by Mitsui Miike Kakoki Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min to obtain a toner 21.
The weight average particle diameter (D4) of the toner 21 was 6.07 μm, and the average circularity was 0.975.

<Production Example of Magnetic Core Particle 1>
・ Step 1 (weighing / mixing step):
62.7 parts of Fe ₂ O ₃ 29.5 parts of MnCO ₃ 6.8 parts of Mg (OH) ₂ 1.0 part of SrCO _{3 A} ferrite raw material was weighed so as to have the above composition ratio. Thereafter, the mixture was pulverized and mixed in a dry vibration mill using stainless steel beads having a diameter of 1/8 inch for 5 hours.
Step 2 (temporary firing step):
The obtained pulverized product was formed into pellets of about 1 mm square with a roller compactor. After removing coarse powder from the pellets with a vibrating sieve having a mesh size of 3 mm and then removing fine powders with a vibrating sieve having a mesh size of 0.5 mm, the pellets were burned in a nitrogen atmosphere (oxygen concentration: 0. (01% by volume) 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 the obtained calcined ferrite was pulverized to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of the calcined ferrite using zirconia beads having a diameter of 1/8 inch, and pulverized for 1 hour with a wet ball mill. . The obtained slurry was pulverized by a wet ball mill using 1/16 inch diameter alumina beads for 4 hours to obtain a ferrite slurry (finely pulverized calcined ferrite).
Step 4 (granulation step):
To a ferrite slurry, 1.0 part of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder are added to 100 parts of calcined ferrite, and the particles are formed into spherical particles with a spray dryer (manufacturer: Okawara Kakoki). Granulated. After the obtained particles were adjusted in particle size, they were heated at 650 ° C. for 2 hours using a rotary kiln to remove organic components of the dispersant and the binder.
Step 5 (firing step):
In order to control the firing atmosphere, the temperature was raised from room temperature to a temperature of 1300 ° C. for 2 hours in a nitrogen atmosphere (oxygen concentration: 1.00% by volume) in an electric furnace, and then fired at a temperature of 1150 ° C. for 4 hours. Thereafter, the temperature was lowered to 60 ° C. over 4 hours, returned from the nitrogen atmosphere to the atmosphere, and taken out at a temperature of 40 ° C. or lower.
Step 6 (sorting step):
After pulverizing the aggregated particles, a low magnetic force product was cut by magnetic separation, and sieved with a 250 μm mesh sieve to remove coarse particles, and a 50% particle size (D50) of 37.0 μm on a volume distribution basis. Magnetic core particles 1 were obtained.

<Preparation of coating resin 1>
Cyclohexyl methacrylate monomer 26.8 parts Methyl methacrylate monomer 0.2 part Methyl methacrylate macromonomer 8.4 parts (macromonomer having a weight average molecular weight of 5000 having a methacryloyl group at one end)
Toluene 31.3 parts Methyl ethyl ketone 31.3 parts Azobisisobutyronitrile 2.0 parts Of the above-mentioned materials, cyclohexyl methacrylate monomer, methyl methacrylate monomer, methyl methacrylate macromonomer, toluene, methyl ethyl ketone, a reflux condenser, a thermometer, The flask was placed in a four-necked separable flask equipped with a nitrogen inlet tube and a stirrer, and nitrogen gas was introduced to make the atmosphere sufficiently nitrogen. Thereafter, the mixture was heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours to carry out polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was separated by filtration and dried in vacuo to obtain a coating resin 1.
Next, 30 parts of the coating resin 1 was dissolved in 40 parts of toluene and 30 parts of methyl ethyl ketone to obtain a 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 part (primary particle diameter 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption) 75mL / 100g)
Was dispersed in a paint shaker for 1 hour using zirconia beads having 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.

<Example of manufacturing magnetic carrier 1>
(Resin coating step):
The magnetic core particles 1 and the coating resin solution 1 were charged into a vacuum degassing kneader maintained at room temperature (the amount of the coating resin solution was 2.5 parts as a resin component with respect to 100 parts of the magnetic core particles 1). Part). After the introduction, the mixture was stirred at a rotation speed of 30 r / min for 15 minutes. After the solvent was volatilized to a certain degree or more (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, and toluene was distilled off over 2 hours, followed by cooling. . The obtained magnetic carrier is subjected to magnetic separation to separate low-magnetic-force products, passed through a sieve having 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. 1 was obtained.

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

<Production Examples of Two-Component Developers 2 to 19>
In the production example of the two-component developer 1, the same operation was performed except that the toner 1 was changed to the toners 2 to 19, and two-component developers 2 to 19 were obtained.

<Example 1>
The following evaluation was performed using the two-component developer 1 described above.
A two-component developer 1 was charged into a developing device at a cyan position using a modified image RUNNER ADVANCE C5560 printer manufactured by Canon Inc. as an image forming apparatus. The modification points of the apparatus were changed so that the fixing temperature, the process speed, the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power could be freely set. 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 amount of applied toner of the FFh image becomes desired. Was done. FFh is a value in which 256 gradations are displayed in hexadecimal, 00h is the first gradation of 256 gradations (white background), and FFh is the 256th gradation of 256 gradations (solid part). .
Evaluation was performed 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: An image of 2 cm x 5 cm is placed at the center of the 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
For stabilization and durability evaluation of the evaluation machine, 30,000 sheets were output on A4 paper using a band chart having an image ratio of 0.1%. Thereafter, 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 transferred to the recording paper. The stopped intermediate transfer body of the evaluation machine was taken out, a transparent adhesive tape was stuck to the transferred image, and a toner was collected. The whole of the adhesive tape was stuck to a recording paper. The density of the image was measured with an optical density system, and the density at the place where only the adhesive tape was stuck on the recording paper was subtracted to obtain the transfer density A.
In addition, the electrostatic latent image carrier of the evaluation machine was taken out, and the residual transfer density B of the residual toner was determined in the same manner.
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 equation. The obtained transfer efficiency was evaluated according to the following evaluation criteria. When the results were A to C, it was evaluated that the effects of the present invention were obtained.
Transfer efficiency = {transfer density A / (transfer density A + transfer residual density B)} × 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%

[Charging 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: An image of 2 cm x 5 cm is placed at the center of the A4 paper. Test environment: High temperature and high humidity environment (temperature 30 ° C / humidity 80% RH (hereinafter H / H))
Process speed: 377mm / sec
As the durability evaluation of the evaluation machine, 30,000 sheets were output on A4 paper 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 (measurement unit) in which an electric field and an acoustic field are simultaneously formed, measures the moving speed of the particles by a laser Doppler method, and measures the particle size and the charge amount. . The sample particles that have entered the measuring section of the apparatus fall while being deviated in the horizontal direction under the influence of the acoustic field and the electric field, 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. When a predetermined number of charge amounts are measured, the screen stops, and thereafter, the three-dimensional distribution of charge amount and particle size, the charge amount distribution by particle size, the average charge amount (coulomb / weight), and the like are displayed. Will be displayed.
The charge amount of the toner was measured by introducing the above-described two-component developer as sample particles into a measurement unit of an Espart analyzer.
The measurement result was substituted into the following equation to calculate the retention of the charge amount of the toner, and evaluated based on the following criteria. Table 5 shows the evaluation results. When the results were A to C, it was evaluated that the effects of the present invention were obtained.
Formula: Friction charge retention of toner (%)
= [Toner charge amount of the above-mentioned durable developer] / [Toner charge amount of the initial developer] × 100
(Evaluation criteria)
A: Toner charge retention of 95% or more B: Toner charge retention of 90% to less than 95% C: Toner charge retention of 80% to less than 90% D: Toner charge retention of less than 80%

Claims (11)

A toner having toner particles and inorganic fine particles,
The resin existing 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 under an environment of 25 ° C., which is measured by a micro-hardness measuring device, and has a plastic deformation. Rate H is 1.0% to 30.0%,
The toner, wherein the inorganic fine particles have a rectangular parallelepiped particle shape.   2. The toner according to claim 1, wherein the resin is present in a region from 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 treating agent satisfy the following expression (1). 4.
| SP1−SP2 | ≦ 1.00 (1) The toner according to any one of claims 1 to 3, wherein a surface potential B obtained by performing a rubbing test using the inorganic fine particles and a resin present on the surface of the toner particles is 100 V or more.
Surface potential B = (Surface potential D of the resin piece measured in a state where the resin particles of the resin present on the surface of the toner particles are rubbed with the inorganic fine particles and then the inorganic fine particles are attached to the resin particles) − (Surface potential E measured using a resin piece obtained by rubbing a resin piece of resin present on the surface of the toner particles with the inorganic fine particles and then removing the inorganic fine particles by air blowing)   The toner according to any one of claims 1 to 4, wherein the inorganic fine particles are strontium titanate.   The toner according to any one of claims 1 to 5, wherein the primary particles of the inorganic fine particles have a number average particle diameter of 10 nm to 250 nm.   The toner according to any one of claims 1 to 6, wherein the resin present on the surface of the toner particles contains an ester group-containing olefin-based copolymer in an amount of 50% by mass or more. The ester group-containing olefin copolymer,
A unit Y1 represented by the following formula (2):
The toner according to claim 7, comprising: a unit represented by the following formula (3) and at least one unit Y2 selected from the group of 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 , and R ⁵ represents CH ₃ or C ₂ H ₅ is shown.)   The ester group concentration of the said ester group containing olefin copolymer is 2.0 mass%-17.9 mass% with respect to the total mass of the said ester group containing olefin copolymer. The toner according to claim 1.   The toner according to claim 1, wherein the inorganic fine particles have a cubic particle shape. The method for producing a toner according to claim 1, wherein:
The production method
A dispersion step of preparing a resin fine particle dispersion,
An aggregation step of aggregating the resin fine particle dispersion to form an aggregate, and
A method for producing a toner, comprising a fusing step of fusing the aggregate by heating.