JP2015230376A - Electrostatic charge image developer, process cartridge, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developer capable of suppressing occurrence of blushing resulting from electric charge leakage after a toner mixture defect and leaving the defect as it is, and a reduction in image density at a time of continuously outputting images at low image density.SOLUTION: An electrostatic charge image developer comprises: a carrier that includes a core material having an electric resistance from 1×10Ωcm to 1×10Ωcm under an electric field of 4800 V/cm at 30°C85%RH, and a covering layer provided on a surface of the core material and containing resin; and a toner including toner particles, first silica particles surface-treated by oil and having a volume mean particle size from 70 nm to 200 nm, and second silica particles surface-treated by oil and having a volume mean particle size from 10 nm to 50 nm.

Description

  The present invention relates to an electrostatic charge image developer, a process cartridge, and an image forming apparatus.

  In electrophotographic image formation, a two-component developer containing toner and a carrier as an image forming material is often used.

As a toner that can be applied to a two-component developer, for example, Patent Document 1 discloses that “a toner base particle containing at least a binder resin and a colorant as a component and an external additive attached to the surface of the base particle. In the toner, the external additive is at least two kinds of silica fine particles and at least one kind of titanium oxide fine particles, and among the silica fine particles, silica fine particles (a) having the smallest BET specific surface area, and then The difference in BET specific surface area of silica fine particles (b) having a small BET specific surface area is 30 m ² / g or more, both of the silica fine particles (a) and (b) are treated with a silane coupling agent, and both are treated with a silicone oil. The oil treatment amount is 2 to 40 parts by mass with respect to 100 parts by mass of the untreated silica fine particle matrix. The oil throughput of the BET specific surface area of 1 m ² per child base silica fine particles (a) is 0.7 times to 90 times the fine silica particles (b), per 100 parts by mass of the toner base particles (a) The added mass part of (b) is 0.2 to 5.0 times the added mass part of the titanium oxide, and the titanium oxide fine particles having the largest BET specific surface area are subjected to at least a coupling treatment. The addition amount of the titanium oxide fine particles per 100 parts by mass of toner base particles is 0.05 to 1.0 part by mass, and the average particle size calculated from the weight particle size distribution of the toner is 3 to 9 μm. , A toner characterized in that the ratio of 12.7 μm or more is 2% or less.

  Further, as a toner that can be applied to a two-component developer, for example, Patent Document 2 discloses that “a toner particle containing at least a binder resin and a colorant and a toner containing silica fine particles, the silica fine particles At least one of silane and silazane, and at least two types of silica fine particles A and silica fine particles B treated with 1.0% by mass or more and 50.0% by mass or less of silicone oil, A toner is proposed in which the immobilization rate of silicone oil is 60% or more on a carbon amount basis, and the silica fine particles B have an immobilization rate of silicone oil of 50% or less on a carbon amount basis. .

JP 2004-126240 A JP 2009-276641 A

  An object of the present invention is to develop an electrostatic charge image that can suppress the occurrence of fogging due to poor toner mixing and leakage of charge after standing, and the reduction in image density when a low image density image is continuously output. Is to provide an agent.

The above problem is solved by the following means. That is,
The invention according to claim 1
A core material having an electric resistance of 1 × 10 ⁷ Ωcm or more and 1 × 10 ¹⁰ Ωcm or less under an electric field of 4800 V / cm at 30 ° C. and 85% RH, and a coating layer containing a resin provided on the surface of the core material; A carrier having
Toner particles, a first silica particle having a volume average particle size of 70 nm to 200 nm that has been surface treated with oil, and a second silica particle having a volume average particle size of 10 nm to 50 nm that has been surface treated with oil A toner having an external additive,
An electrostatic charge image developer.

The invention according to claim 2
The electrostatic charge image developer according to claim 1, wherein the amount of oil liberated in the first silica particles in the toner is 3% by mass or more and 20% by mass or less.

The invention according to claim 3
The electrostatic image developer according to claim 1, wherein the toner particles in the toner are toner particles obtained by a wet manufacturing method.

The invention according to claim 4
The electrostatic image developer according to claim 1 is contained, and the electrostatic image formed on the surface of the image carrier is developed as a toner image by the electrostatic image developer. With developing means,
It is a process cartridge that can be attached to and detached from the image forming apparatus.

The invention according to claim 5
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
An electrostatic image developer according to any one of claims 1 to 3 is accommodated, and the electrostatic image formed on the surface of the image carrier is developed as a toner image by the electrostatic image developer. Developing means,
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus.

According to the first aspect of the present invention, when the electrical resistance as described above of the core material is less than 1 × 10 ⁷ Ωcm, the second silica particle size is out of the above range, Compared with the case where the particle size of the silica particles is out of the above range, or when the surface treatment agent of the first silica particles or the second silica particles is only hexamethyldisilazane (HMDS), the toner mixing is poor and Provided is an electrostatic charge image developer capable of suppressing the occurrence of fog due to charge leakage after being left and the decrease in image density when an image having a low image density is continuously output.
According to the second aspect of the present invention, compared to the case where the oil release amount of the first silica particles is out of the above range, the electrostatic charge that can suppress the decrease in the image density when the image having a low image density is continuously output. An image developer is provided.
According to the third aspect of the present invention, compared to the case where the toner particles are toner particles produced by a dry process, the occurrence of fogging due to poor toner mixing and leakage of charges after being left, and the image having a low image density are continuously displayed. Provided is an electrostatic charge image developer capable of suppressing a decrease in image density upon output.

According to the invention according to claim 4 or 5, when the electrical resistance as described above of the core material is less than 1 × 10 ⁷ Ωcm, when the particle size of the first silica particles is out of the above range, Compared with the case where the particle diameter of the second silica particles is out of the above range, or when the surface treatment agent of the first silica particles or the second silica particles is only hexamethyldisilazane (HMDS). A process cartridge using an electrostatic charge image developer capable of suppressing the occurrence of fogging due to poor mixing and leakage of charge after standing and the reduction of image density when continuously outputting low image density images; Alternatively, an image forming apparatus is provided.

1 is a schematic configuration diagram illustrating an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows the process cartridge which concerns on this embodiment.

  The electrostatic charge image developer, process cartridge, and image forming apparatus of the present invention will be described in detail with reference to an exemplary embodiment.

<Electrostatic image developer>
The electrostatic charge image developer according to the exemplary embodiment (hereinafter may be simply referred to as “developer”) has an electric resistance of 1 × 10 ⁷ Ωcm or more in an electric field of 4800 V / cm at 30 ° C. and 85% RH. × 10 ¹⁰ Ωcm or less core material, carrier having a coating layer containing a resin provided on the surface of the core material, toner particles, and volume average particle size surface-treated with oil is 70 nm or more First silica particles of 200 nm or less (hereinafter may be simply referred to as “first silica particles”), and second silica particles having a volume average particle diameter of 10 nm to 50 nm surface-treated with oil ( Hereinafter, a toner having an external additive that may be simply referred to as “second silica particles” is included.
The electrostatic charge image developer having the above configuration suppresses the occurrence of fogging due to poor toner mixing and leakage of charge after being left, and lowers the image density when continuously outputting low image density images. Can also be suppressed.
Here, “fogging” refers to a phenomenon in which toner adheres to a non-image portion.

Conventionally, as toner in a developer, toner using silica particles surface-treated with oil (hereinafter sometimes referred to as “oil-treated silica particles”) as an external additive is known.
The oil used for the surface treatment has a property of easily adsorbing moisture, and the oil-treated silica particles adsorb moisture in the air, and the oil portion that has adsorbed the moisture serves as a conduction path for charges. As a result, the toner particles to which the oil-treated silica particles are externally added improve the charge exchange property between adjacent toner particles, so that a large amount of toner is consumed and an image with a high image density (image density of 20% or more) is output. Even if the toner continues, it is difficult for mixing failure (admixability failure) between the existing toner and the replenished toner, and the charge level of the replenished toner can quickly reach the charge level of the existing toner. .
For this reason, even when the output of an image with a high image density is continuous as described above, the occurrence of fogging due to poorly charged toner caused by poor toner mixing is suppressed.

However, under a high temperature and high humidity environment (28 ° C. and 85% RH), when the oil of the oil-treated silica particles moves to the carrier, the oil adsorbs moisture and becomes a charge leakage site in the carrier. Charges may leak.
For this reason, if the image is output after being left in a high-temperature and high-humidity environment and the developer has not moved, the charge leakage from the carrier occurs during the standing time. The fog may be caused by.
In order to suppress fogging caused by the carrier as described above, a method of increasing the resistance of the core material of the carrier can be mentioned. By increasing the resistance of the core material of the carrier, the leakage of electric charge can be suppressed even when the oil of the oil-treated silica particles moves to the surface of the carrier.
On the other hand, when the output of an image having a low image density (image density of 1% or less) is continuous, the developer temperature rises, and when the amount of water in the developer decreases, the charging ability of the toner particles increases. Also, there are few charge leakage sites in the carrier. As a result, when the output of low image density images continues, a phenomenon that the developer charge increases excessively (hereinafter referred to as charge-up) occurs, and a phenomenon such as a decrease in image density due to deterioration in developability occurs. It will occur.

As described above, in a conventional developer including a toner using oil-treated silica particles as an external additive, generation of fog due to toner mixing failure, occurrence of fog due to charge leakage after being left, Further, it has not been possible to suppress all of the decrease in image density due to charge-up.
On the other hand, the developer according to the present embodiment combines the carrier including a core material having a specific electric resistance with the toner using oil-treated silica having different particle diameters as an external additive. Generation of fog and a decrease in image density can be suppressed.

The mechanism for obtaining such an effect is not necessarily clear, but is presumed as follows.
The first silica particles and the second silica particles are both oil-treated silica particles, and a charge conduction path is formed when moisture is adsorbed on the oil on the surface, and fog caused by poor mixing of toner is formed. Occurrence can be suppressed. In particular, since the second silica particles have a small particle size, they are difficult to separate from the surface of the toner particles and easily form a state in which oil is applied to the surface of the toner particles. Since the efficiency is improved, it is possible to suppress the occurrence of fogging due to toner mixing failure.
In addition, since the electrical resistance of the core material of the carrier is high as described above, even if the oil moves from the first silica particle and the second silica particle to the surface of the carrier, the leakage of the charge after being left is left. Occurrence of fogging due to this can be suppressed.
The first silica particles have a larger diameter than the second silica particles, are easily detached from the surface of the toner particles, easily move to the surface of the carrier, and easily form a state where oil is applied to the surface of the carrier.
Due to the presence of the first silica particles and the second silica particles, oil can be applied to both the surface of the toner particles and the surface of the carrier, so that the water adsorption ability of the developer as a whole is increased.
As a result, even when low-image-density images are output continuously and the developer temperature rises, it is possible to suppress the developer chargeability from increasing due to the presence of moisture adsorbed on the oil (charging ability). Is controlled to be low), and it is considered that the decrease in image density due to the charge-up of the developer can be suppressed.

  Hereinafter, the carrier and toner constituting the electrostatic charge image developer according to the exemplary embodiment will be described in detail.

[Carrier]
The carrier includes a core material having an electric resistance of 1 × 10 ⁷ Ωcm or more and 1 × 10 ¹⁰ Ωcm or less under an electric field of 4800 V / cm at 30 ° C. and 85% RH, and a resin provided on the surface of the core material. And a coating layer.

−Core material−
In the present embodiment, if the value of the electrical resistance of the core material is less than 1 × 10 ⁷ Ωcm, it is difficult to suppress the leakage of charges when the developer is left, and fogging due to the leakage of charges may occur. is there. Moreover, when the value of the electrical resistance of the core material exceeds 1 × 10 ¹⁰ Ωcm, charge-up easily occurs, and even when using the first silica particles and the second silica particles which are oil-treated silica particles described later, It becomes difficult to suppress a decrease in image density due to charge-up.
The value of the electrical resistance of the core material is 1 × 10 ⁸ Ωcm or more and 5 × 10 ⁹ Ωcm or less from the viewpoint that fogging and lowering of the image density when images with low image density are continuously output can be further suppressed. Is preferably 5 × 10 ⁸ Ωcm or more and 1 × 10 ⁹ Ωcm or less.

The electrical resistance (volume electrical resistance) of the core material is measured as follows.
A core material to be measured is placed flat on the surface of a circular jig provided with a 20 cm ² electrode plate so as to have a thickness of about 1 mm to 3 mm, thereby forming a core material layer. On top of this, the same electrode plate of 20 cm ² is placed and the core material layer is sandwiched. In order to eliminate the space between the core materials, a thickness of 4 mm is applied to the electrode plate placed on the core material layer, and then the thickness (mm) of the core material layer is measured. Both electrodes above and below the core material layer are connected to an electrometer and a high-voltage power generator. A high voltage is applied to both electrodes so that the electric field is 10 ^3.8 V / cm, and the current value (A) flowing at this time is read to calculate the resistance (volume electrical resistance, Ωcm) of the core material. . The calculation formula for the resistance (Ωcm) of the core is as shown in the following formula (1).
R = E × 20 / (I−I ₀ ) / L (1)
In the above formula (1), R is the resistance (Ωcm) of the core material, E is the applied voltage (V), I is the current value (A), I ₀ is the current value (A) at the applied voltage of 0 V, and L is the core material. Each represents the thickness (mm) of the layer. A coefficient of 20 represents the area (cm ² ) of the electrode plate.
The measurement environment is a temperature of 30 ° C. and a humidity of 85% RH.

Here, when measuring the electrical resistance of the core material from the carrier provided with the coating layer, a method of separating the core material by the following method may be used.
That is, it is a method of separating the core material by dissolving or thermally decomposing only the coating layer from the carrier provided with the coating layer in the same manner as when measuring the coating amount of the coating layer on the core material described later. .

As the core material, known magnetic particles are used, and examples thereof include particles of magnetic metals such as iron, nickel and cobalt, and magnetic oxides such as ferrite and magnetite.
Among these, ferrite particles are preferable because the above-described electric resistance can be easily obtained and magnetic characteristics can be easily controlled.
The ferrite particles are not particularly limited, and examples thereof include ferrite particles represented by the following general formula (2).
_{(MO) X (Fe 2 O} 3) Y ··· formula (2)
(In General Formula (2), M contains at least one selected from Cu, Zn, Fe, Mg, Mn, Ca, Li, Ti, Ni, Sn, Sr, Al, Ba, Co, Mo, and the like. Moreover, X and Y indicate mass molar ratios and satisfy X + Y = 100).
Among those represented by the general formula (2), Cu, Zn, Fe, Mn, Mg, Sr, and Cu are preferable from the viewpoint of optimizing magnetic characteristics and electric resistance.

The volume average particle size of the core material is preferably 10 μm or more and 500 μm or less, more preferably 30 μm or more and 150 μm or less, and particularly preferably 30 μm or more and 100 μm or less.
The volume average particle diameter is a value measured using a laser diffraction / scattering particle size distribution analyzer (LS Particle Size Analyzer: LS13 320, manufactured by BECKMAN COULTER). For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution is subtracted from the small particle size side, and the particle size at 50% cumulative is taken as the volume average particle size.

-Coating layer-
The resin for coating the core material (hereinafter referred to as “coating resin”) is not particularly limited and is selected according to the purpose.
Examples of the coating resin include polyolefin resins such as polyethylene and polypropylene; polyvinyl resins such as polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, and polyvinyl ketone. Resin and polyvinylidene resin; vinyl chloride, vinyl acetate copolymer; styrene, acrylic acid copolymer; straight silicone resin composed of organosiloxane bond or modified product thereof; polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychloro Fluorocarbon resin such as trifluoroethylene; silicone resin; polyester; polyurethane; polycarbonate; phenolic resin; Fat, melamine resins, benzoguanamine resins, urea resins, amino resins such as polyamide resins, epoxy resins, per se known resins and the like. These coating resins may be used alone or in combination of two or more.

The coating layer may contain conductive particles.
Here, the conductivity means that the volume resistivity is less than 10 ⁷ Ω · cm. Conductive particles include metal particles such as gold, silver and copper; carbon black particles; semiconductive oxide particles such as titanium oxide and zinc oxide; titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate And particles having the surface of powder or the like covered with tin oxide, carbon black, metal, or the like. These may use 1 type and may use multiple types.
Among the above, carbon black particles are preferable. The type of carbon black is not particularly limited, but carbon black having a DBP oil absorption of 50 ml / 100 g or more and 250 ml / 100 g or less is desirable.

The coating layer may contain a wax. The wax is not particularly limited, and examples thereof include low molecular weight polyolefin wax, carnauba wax, rice wax, candelilla wax, paraffin wax, microcrystal wax, Fischer-Tropsch wax, and solid acid ester wax. Paraffin wax and Fischer-Tropsch wax are particularly desirable.
One type of wax may be used, or a plurality of types may be used.

The thickness of the coating layer is not particularly limited, but is preferably 0.1 μm or more and 3.0 μm or less, more preferably 0.2 μm or more and 2.0 μm or less, and further preferably 0.2 μm or more and 1.0 μm or less. .
The thickness of the coating layer is measured by the following method.
30 parts by mass of carrier is added to 70 parts by mass of a mixed liquid of two-part adhesive quick 30 (manufactured by Konishi Co., Ltd.), and further mixed, and left to stand at 25 ° C. for 48 hours to be cured. The cured embedded material is shaped with a razor, and then cut with an ultramicrotome apparatus (LEICA, URUTRACUT UCT) equipped with a diamond knife SK2035 (Sumitomo Electric Industries, Ltd.). Further, while confirming the smoothness of the cut surface with an optical microscope, cutting is performed until a smooth cut surface is formed, thereby producing a test piece. The obtained test piece is observed with a scanning electron microscope to obtain a cross-sectional image of the test piece. The obtained image was taken into image analysis software WinROOF (manufactured by Mitani Corporation) and converted into a monochrome image, and then the thickness of four coating layers was measured at 90 ° intervals for one randomly selected core material. This is done for 50 pieces, and the arithmetic average is calculated.

The coating amount of the coating layer on the core material is preferably 0.5% by mass or more, more preferably 0.7% by mass or more and 6% by mass or less, and more preferably 1.0% by mass or more and 5.% by mass with respect to the mass of the entire carrier. 0% by mass or less is more desirable.
Here, the coating amount is obtained as follows.
When the coating layer is soluble in the solvent, the carrier is put into a soluble solvent (for example, toluene), the core material is held with a magnet, and the solution in which the coating layer is dissolved is washed away. By repeating this several times, the core material from which the coating layer has been removed remains. The core material is dried and the mass of the core material is measured. The coating amount is calculated by dividing the difference between the carrier amount and the core material amount measured in advance by the carrier amount.
When the coating layer is solvent-insoluble, use a differential type differential thermal balance (eg, differential type differential thermal balance TG8120 manufactured by Rigaku Corporation) and heat in a range of 25 ° C. to 1000 ° C. in a nitrogen atmosphere. Then, the coating amount is calculated from the mass decrease.

(Carrier manufacturing method)
An example of the manufacturing method of the carrier used for this embodiment is demonstrated.
As a manufacturing method of a core material, the following method is mentioned, for example.
First, an appropriate amount of the metal oxide that is the raw material of the core material is blended, pulverized and mixed with a wet ball mill or the like, then granulated and dried with a spray dryer or the like, and then pre-fired using a rotary kiln or the like for magnetic oxidation. Get things. The temperature for the preliminary firing varies depending on the material used, but for example, 500 ° C. or more and 1200 ° C. or less (desirably 600 ° C. or more and 1000 ° C. or less) is preferable. Pre-baking is preferably performed 0 to 3 times as necessary, and stepwise.

Thereafter, the obtained magnetic oxide (preliminarily fired product) is dispersed in water and pulverized with a wet ball mill or the like. The temporarily fired product is pulverized firmly, for example, until the volume average particle size of the pulverized magnetic oxide product (magnetic powder) is in the range of 1.0 μm to 3.0 μm.
The slurry (aqueous dispersion of magnetic oxide pulverized product) obtained by the pulverization was granulated and dried using a spray drier, etc., and then calcined while controlling the oxygen concentration for the purpose of adjusting magnetic properties and resistance. Thereafter, it is pulverized and further classified into a desired particle size distribution to obtain a core material. The firing temperature is, for example, 900 ° C. or higher and 1300 ° C. or lower. Further, it is desirable that the firing atmosphere in the main firing has an oxygen concentration lower than that of the air component.
As described above, the core material is obtained by pulverization and firing.

  In the core material manufacturing method, as a method for adjusting the electric resistance, it is preferable to employ a method of controlling the oxidation state of the core material surface of the carrier from the viewpoint of optimizing the electric resistance and the magnetic characteristics.

Then, the formation method of a coating layer is demonstrated.
For the formation of the coating layer, a method of coating the surface of the core material using a coating solution for forming a coating layer in which a resin and, if necessary, various additives are dissolved in an appropriate solvent may be used.
The solvent is not particularly limited, and may be selected in consideration of the resin to be used, application suitability, and the like.
Specific coating methods for the coating layer forming coating solution include a dipping method in which the core material is immersed in the coating layer forming coating solution, a spray method in which the coating layer forming coating solution is sprayed on the surface of the core material, and a core material. The fluidized bed method in which the coating layer forming coating solution is sprayed in a state where the coating layer is suspended by flowing air, the kneader coater method in which the core material and the coating layer forming coating solution are mixed in the kneader coater, and the solvent is removed. It is done.

  Examples of the volume average particle size of the carrier obtained as described above include a range of 20 μm to 75 μm, and a range of 25 μm to 50 μm is more desirable.

〔toner〕
The toner according to the exemplary embodiment includes toner particles, first additive silica particles having a volume average particle size of 70 nm or more and 200 nm or less that are surface-treated with oil, and a volume average particle size that is surface-treated with oil. And second silica particles having a size of 10 nm or more and 50 nm or less.

(First silica particles and second silica particles)
The first silica particles and the second silica particles used as external additives will be described.
Although the first silica particles and the second silica particles have different particle diameters, both are silica particles surface-treated with oil.

-Silica particles-
The silica particles may be fumed silica, colloidal if the first silica particles have a volume average particle size of 70 nm to 200 nm, and the second silica particles have a volume average particle size of 10 nm to 50 nm. Silica particles such as silica and silica gel are used without particular limitation.

In the present embodiment, the volume average particle diameter of the first silica particles is 70 nm or more and 200 nm or less, preferably 80 nm or more and 160 nm or less, more preferably 90 nm or more and 140 nm or less.
When the volume average particle diameter of the first silica particles exceeds 200 nm, the carrier is easily detached from the surface, the coverage of the surface of the carrier of the first silica particles is also reduced, and the developer is charged up. It is difficult to suppress a decrease in image density.
Further, when the volume average particle diameter of the first silica particles is less than 70 nm, it becomes difficult to separate from the toner particles, the coverage of the surface of the carrier of the first silica particles is lowered, and the developer is charged up. It is difficult to suppress the resulting decrease in image density.

In the present embodiment, the volume average particle diameter of the second silica particles is 10 nm or more and 50 nm or less, preferably 10 nm or more and 45 nm or less, and more preferably 20 nm or more and 40 nm or less. If the particle diameter is less than 10 nm, the toner particles are buried in the toner particles, and it is difficult for moisture to be absorbed in the oil, and it is difficult to form a conduction path for the charge, and fogging due to poor toner mixing may occur. is there.
When the volume average particle diameter of the second silica particles exceeds 50 nm, the toner particles are easily separated from the toner particles, and it is difficult to form a charge conduction path on the surface of the toner particles, and fogging due to poor toner mixing occurs. May occur.

The particle size of the silica particles is measured as follows.
That is, 100 primary particles of silica particles are observed with a SEM (Scanning Electron Microscope) apparatus.
The longest diameter and the shortest diameter of each particle are measured by image analysis of primary particles, and the equivalent sphere diameter is measured from this intermediate value. The 50% diameter (D50v) in the cumulative frequency of the obtained sphere equivalent diameter on a volume basis is defined as the volume average particle diameter of the silica particles.

-Surface treatment with oil-
As the oil for surface treatment of the first silica particles and the second silica particles, for example, silicone oil is preferable from the viewpoint of forming a charge conduction path by adsorbing moisture.
Specific examples of the silicone oil include, for example, dimethyl silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, epoxy-modified silicone oil, fluorine-modified silicone oil, alcohol-modified silicone oil, polyether-modified silicone oil, Methyl phenyl silicone oil, methyl hydrogen silicone oil, mercapto modified silicone oil, higher fatty acid modified silicone oil, phenol modified silicone oil, methacrylic acid modified silicone oil, polyether modified silicone oil, methyl styryl modified silicone oil and the like can be used.
The oil used for the surface treatment may be used alone or in combination of two or more.
The oil used for the surface treatment is preferably the same for the first silica particles and the second silica particles, but may be different.

Silica particles can be surface-treated with oil as a dry method such as spray-drying method in which oil or a solution containing oil is sprayed on inorganic particles suspended in a gas phase, or a treatment agent (solution) containing oil. Examples thereof include a wet method in which silica particles are immersed and dried, and a mixing method in which a treating agent and silica particles are mixed with a mixer.
After performing the surface treatment by such a method, residual oil or low boiling point residue may be removed by immersing again in a solvent such as ethanol and drying the solvent.

  In the surface treatment with oil, the amount (use amount) of the oil with respect to the silica particles is preferably 1% by mass or more and 30% by mass or less with respect to the mass of the silica particles from the viewpoint of charging characteristics. % To 15% by mass, more preferably 5% to 12% by mass.

In the first silica particles, the oil liberation amount is preferably 3% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and more preferably 5% by mass or more and 10% by mass or less. More preferably.
Due to the fact that the oil release amount of the first silica particles is 3% by mass or more, sufficient oil is applied to the surface of the carrier, and the chargeability of the developer is controlled to be low, resulting in charge-up. The reduction in image density can be suppressed.
When the amount of oil liberated by the first silica particles is 20% by mass or less, an excessive decrease in charging ability due to the excessive amount of oil applied to the surface of the carrier is suppressed, and leakage of charges after being left standing is prevented. It is easy to suppress the occurrence of fogging.

  In the second silica particles, the oil release amount is preferably 0.5% by mass or more and 15% by mass or less, and 0.5% by mass or more from the viewpoint of maintainability of the oil component on the toner surface. More preferably, it is 10 mass% or less.

The amount of oil liberated from the silica particles is measured as follows.
The silica particles surface-treated with oil are subjected to proton NMR measurement using AL-400 (magnetic field 9.4T (H nucleus 400 MHz) manufactured by JEOL). A sample, a deuterated chloroform solvent, and TMS as a reference substance are filled into a sample tube (diameter 5 mm) made of zirconia. This sample tube is set, for example, frequency: Δ87 kHz / 400 MHz (= Δ20 ppm), measurement temperature: 25 ° C., number of integrations: 16 times, resolution 0.24 Hz (about 32000 points) The peak intensity is converted into the amount of liberated oil using a calibration curve.
For example, when dimethyl silicone oil is used as the oil, NMR measurement of untreated silica particles and dimethyl silicone oil (fluctuate about 5 levels) is performed, and a calibration curve between the oil release amount and the NMR peak intensity is obtained. Should be created.

  In addition, when increasing the amount of oil liberated from the silica particles, the oil treatment is performed multiple times, and when reducing the amount of oil liberated from the silica particles, the step of drying after immersion in the solvent is repeated. It can be controlled by executing.

The first silica particles and the second silica particles may be subjected to a hydrophobization treatment with a silane coupling agent or the like, for example, similarly to other external additives described later.
When performing the hydrophobization treatment, a hydrophobization treatment agent such as a silane coupling agent is contained in the solution or treatment agent containing the oil described above, and the surface treatment may be performed using this.

-Mixing ratio-
The blending ratio of the first silica particles and the second silica particles is such that the amount of the oil component on the toner surface and the carrier surface is controlled, so that the first silica particles / second silica particles = 0.3 or more and 12 The following is good, preferably 0.5 or more and 8 or less, more preferably 1 or more and 5 or less.

The external addition amount of the first silica particles is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1.0% by mass or more and 3% by mass or less with respect to the toner particles from the viewpoint of controlling the amount of oil component on the carrier surface. The mass% or less is more preferable.
The external addition amount of the second silica particles is preferably 0.1% by mass or more and 3.0% by mass or less, and preferably 0.15% by mass with respect to the toner particles from the viewpoint of controlling the amount of the oil component on the toner surface. More preferred is 2.0% by mass or less.

  In addition, when using together the 1st silica particle and the 2nd silica particle, and the other external additive mentioned later, the combination ratio is the total amount of the 1st silica particle and the 2nd silica particle / other external additives. The total amount of the agent is 0.3 to 5 and preferably 1.0 to 3.0.

(Toner particles)
The toner particles include, for example, a binder resin and, if necessary, a colorant, a release agent, and other additives.
In the present embodiment, the toner particles are preferably toner particles obtained by a wet manufacturing method.
Toner particles obtained by a wet process are toner particles that contain a large amount of water and whose charging performance is likely to change due to the desorption of the water. Therefore, by externally adding the first silica particles and the second silica particles described above to the toner particles obtained by the wet manufacturing method, the occurrence of fog and the image density due to the first silica particles and the second use. It is easy to exhibit the effect of suppressing the decrease in the temperature.

-Binder resin-
Examples of the binder resin include styrenes (eg, styrene, parachlorostyrene, α-methylstyrene, etc.), (meth) acrylic acid esters (eg, methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid). n-butyl, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (for example, acrylonitrile, Methacrylonitrile, etc.), vinyl ethers (eg, vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), olefins (eg, ethylene, propylene, etc.) Emissions, a homopolymer of a monomer such as butadiene) and the like, or a vinyl-based resin composed of these monomers with two or more combinations copolymer.
As the binder resin, for example, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, non-vinyl resin such as modified rosin, a mixture of these with the vinyl resin, or these Examples also include a graft polymer obtained by polymerizing a vinyl monomer in the coexistence.
These binder resins may be used alone or in combination of two or more.

A polyester resin is suitable as the binder resin.
Examples of the polyester resin include known polyester resins.

  As a polyester resin, the condensation polymer of polyhydric carboxylic acid and polyhydric alcohol is mentioned, for example. In addition, as a polyester resin, a commercial item may be used and what was synthesize | combined may be used.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids (eg, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, sebacic acid, etc.) Alicyclic dicarboxylic acids (for example, cyclohexanedicarboxylic acid), aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.), their anhydrides, or lower (for example, having 1 or more carbon atoms) 5 or less) alkyl esters. Among these, as polyvalent carboxylic acid, aromatic dicarboxylic acid is preferable, for example.
The polyvalent carboxylic acid may be used in combination with a dicarboxylic acid or a trivalent or higher carboxylic acid having a crosslinked structure or a branched structure. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, anhydrides thereof, or lower (eg, having 1 to 5 carbon atoms) alkyl ester.
Polyvalent carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyhydric alcohol include aliphatic diols (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (for example, cyclohexanediol, cyclohexanedimethanol, Hydrogenated bisphenol A, etc.) and aromatic diols (for example, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc.). Among these, as the polyhydric alcohol, for example, aromatic diols and alicyclic diols are preferable, and aromatic diols are more preferable.
As the polyhydric alcohol, a trihydric or higher polyhydric alcohol having a crosslinked structure or a branched structure may be used together with the diol. Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, and pentaerythritol.
A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

The glass transition temperature (Tg) of the polyester resin is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, described in the method for determining the glass transition temperature in JIS K-1987 “Method for Measuring Transition Temperature of Plastics”. It is determined by “extrapolated glass transition start temperature”.

The weight average molecular weight (Mw) of the polyester resin is preferably from 5,000 to 1,000,000, more preferably from 7,000 to 500,000.
The number average molecular weight (Mn) of the polyester resin is preferably from 2,000 to 100,000.
The molecular weight distribution Mw / Mn of the polyester resin is preferably 1.5 or more and 100 or less, and more preferably 2 or more and 60 or less.
The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120GPC as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result.

The polyester resin is obtained by a well-known manufacturing method. Specifically, for example, the polymerization temperature is set to 180 ° C. or higher and 230 ° C. or lower, the pressure in the reaction system is reduced as necessary, and the reaction is performed while removing water and alcohol generated during the condensation.
In addition, when the monomer of the raw material is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added and dissolved as a solubilizing agent. In this case, the polycondensation reaction is performed while distilling off the solubilizer. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polymerized together with the main component. It is good to condense.

  The content of the binder resin is, for example, preferably 40% by weight to 95% by weight, more preferably 50% by weight to 90% by weight, and more preferably 60% by weight to 85% by weight with respect to the entire toner particles. Further preferred.

-Colorant-
Examples of the colorant include carbon black, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, brilliant. Carmine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Pigment Red, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Pigment Blue, Phthalocyanine Green, Various pigments such as malachite green oxalate, or acridine series, xanthene series, azo series Various dyes such as benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, and thiazole Can be mentioned.
A colorant may be used individually by 1 type and may use 2 or more types together.

  As the colorant, a surface-treated colorant may be used as necessary, or it may be used in combination with a dispersant. A plurality of colorants may be used in combination.

  The content of the colorant is, for example, preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 15% by mass or less with respect to the entire toner particles.

-Release agent-
Examples of release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; and ester waxes such as fatty acid esters and montanic acid esters. And so on. The release agent is not limited to this.

The melting temperature of the release agent is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.
The melting temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC) according to the “melting peak temperature” described in JIS K-1987 “Method for measuring the transition temperature of plastics”.

  The content of the release agent is, for example, preferably 1% by mass to 20% by mass and more preferably 5% by mass to 15% by mass with respect to the entire toner particles.

-Other additives-
Examples of other additives include known additives such as a magnetic material, a charge control agent, and inorganic powder. These additives are contained in the toner particles as internal additives.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
Here, the core / shell structure toner particles include, for example, a core portion including a binder resin and, if necessary, other additives such as a colorant and a release agent, and a binder resin. It is good to be comprised with the comprised coating layer.

  The volume average particle diameter (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

In addition, various average particle diameters and various particle size distribution indexes of the toner particles are measured using Coulter Multisizer II (manufactured by Beckman-Coulter), and the electrolyte is measured using ISOTON-II (manufactured by Beckman-Coulter). The
In the measurement, 0.5 mg to 50 mg of a measurement sample is added as a dispersant to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate). This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolyte in which the sample is suspended is dispersed for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm to 60 μm is obtained using a 100 μm aperture with a Coulter Multisizer II. taking measurement. The number of particles to be sampled is 50,000.
A cumulative distribution is drawn from the smaller diameter side to the particle size range (channel) divided based on the measured particle size distribution, and the cumulative particle size of 16% is the volume particle size D16v. D16p, a particle size that is 50% cumulative is defined as a volume average particle size D50v, a cumulative number average particle size D50p, and a particle size that is 84% cumulative is defined as a volume particle size D84v and a number particle size D84p.
Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D84p / D16p) ^1/2 .

  The shape factor SF1 of the toner particles is preferably 110 or more and 150 or less, and more preferably 120 or more and 140 or less.

The shape factor SF1 is obtained by the following formula.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.
Specifically, the shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows. That is, by capturing an optical microscope image of particles dispersed on the surface of a slide glass into a Luzex image analyzer using a video camera, obtaining the maximum length and projected area of 100 particles, calculating by the above formula, and obtaining the average value can get.

(Other external additives)
In the toner according to this exemplary embodiment, at least the first silica particles and the second silica particles are externally added to the toner particles, but other external additives may be used in combination.

Examples of other external additives include inorganic particles. As the inorganic particles, TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na ₂ O, ZrO ₂ , CaO · SiO ₂ , Examples thereof include particles such as K ₂ O. (TiO ₂ ) _n , Al ₂ O ₃ .2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , and MgSO ₄ .
Silica particles different from the first silica particles and the second silica particles described above may also be used as other external additives as long as the effects of the developer according to this embodiment are not impaired.

The surface of the inorganic particles as another external additive is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually, for example, 1 part by mass or more and 10 parts by mass with respect to 100 parts by mass of the inorganic particles.

  Other external additives include resin particles (resin particles such as polystyrene, PMMA, and melamine resin), cleaning activators (for example, metal salts of higher fatty acids represented by zinc stearate, particles of fluorine-based high molecular weight). And so on.

  The amount of other external additives added is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 2.0% by mass or less with respect to the toner particles.

[Toner Production Method]
Next, a toner manufacturing method according to this embodiment will be described.
The toner according to the exemplary embodiment can be obtained by externally adding an external additive to the toner particles after the toner particles are manufactured.

The toner particles may be produced by any one of a dry production method (for example, a kneading pulverization method) and a wet production method (for example, an aggregation coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). The production method of the toner particles is not particularly limited, and a known production method is adopted.
Among these, it is preferable to obtain toner particles by an aggregation and coalescence method.

Specifically, for example, when toner particles are produced by an aggregation coalescence method,
A step of preparing a resin particle dispersion in which resin particles to be a binder resin are dispersed (resin particle dispersion preparation step), and a resin particle dispersion (after mixing other particle dispersions as necessary) In the dispersion), the resin particles (other particles as necessary) are aggregated to form aggregated particles (aggregated particle formation step), and the aggregated particle dispersion in which the aggregated particles are dispersed is heated. Then, toner particles are manufactured through a process of fusing and coalescing the aggregated particles to form toner particles (fusing and coalescing process).

Details of each step will be described below.
In the following description, a method of obtaining toner particles containing a colorant and a release agent will be described. However, the colorant and the release agent are used as necessary. Of course, you may use other additives other than a coloring agent and a mold release agent.

-Preparation step of resin particle dispersion-
First, together with a resin particle dispersion in which resin particles serving as a binder resin are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed and a release agent particle dispersion in which release agent particles are dispersed are prepared. To do.

  Here, the resin particle dispersion is prepared, for example, by dispersing resin particles in a dispersion medium using a surfactant.

Examples of the dispersion medium used for the resin particle dispersion include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an anionic surfactant and a cationic surfactant are particularly mentioned. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant.
Surfactant may be used individually by 1 type and may use 2 or more types together.

Examples of the method for dispersing the resin particles in the dispersion medium in the resin particle dispersion include a general dispersion method such as a rotary shear homogenizer, a ball mill having media, a sand mill, and a dyno mill. Depending on the type of resin particles, the resin particles may be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method.
The phase inversion emulsification method is a method in which a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, and a base is added to the organic continuous phase (O phase) to neutralize the aqueous medium. (W phase) is added to convert the resin from W / O to O / W (so-called phase inversion) to form a discontinuous phase and disperse the resin in an aqueous medium in the form of particles. It is.

The volume average particle size of the resin particles dispersed in the resin particle dispersion is preferably 0.01 μm or more and 1 μm or less, more preferably 0.08 μm or more and 0.8 μm or less, and even more preferably 0.1 μm or more and 0.6 μm. .
In addition, the volume average particle diameter of the resin particles is a particle size range (channel) divided by using a particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring apparatus (for example, LA-700 manufactured by Horiba, Ltd.). The cumulative distribution is subtracted from the small particle diameter side with respect to the volume, and the particle diameter that becomes 50% cumulative with respect to all the particles is measured as the volume average particle diameter D50v. The volume average particle size of particles in other dispersions is also measured in the same manner.

  As content of the resin particle contained in a resin particle dispersion liquid, 5 to 50 mass% is preferable, for example, and 10 to 40 mass% is more preferable.

  For example, a colorant particle dispersion and a release agent particle dispersion are also prepared in the same manner as the resin particle dispersion. In other words, regarding the volume average particle diameter of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles, the colorant particles dispersed in the colorant particle dispersion and the release agent particle dispersion The same applies to the release agent particles to be dispersed.

-Aggregated particle formation process-
Next, the colorant particle dispersion and the release agent particle dispersion are mixed together with the resin particle dispersion.
Then, in the mixed dispersion, resin particles, colorant particles, and release agent particles are hetero-aggregated to have resin particles, colorant particles, and release agent particles having a diameter close to the diameter of the target toner particles. Aggregated particles are formed.

Specifically, for example, the flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, the pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. The resin particles are heated to a glass transition temperature (specifically, for example, the glass transition temperature of the resin particles −30 ° C. or more and the glass transition temperature −10 ° C. or less), and the particles dispersed in the mixed dispersion liquid are aggregated. , Forming aggregated particles.
In the agglomerated particle forming step, for example, the aggregating agent is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is acidic (for example, the pH is 2 or more and 5 or less). ), And after adding a dispersion stabilizer as necessary, the heating may be performed.

Examples of the flocculant include surfactants having a polarity opposite to that of the surfactant used as the dispersant added to the mixed dispersion, for example, inorganic metal salts and divalent or higher-valent metal complexes. In particular, when a metal complex is used as the flocculant, the amount of the surfactant used is reduced, and the charging characteristics are improved.
If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used. As this additive, a chelating agent is preferably used.

Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic substances such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers.
A water-soluble chelating agent may be used as the chelating agent. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and the like.
The addition amount of the chelating agent is, for example, preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass with respect to 100 parts by mass of the resin particles.

-Fusion / unification process-
Next, the aggregated particle dispersion in which the aggregated particles are dispersed is heated to, for example, a glass transition temperature or higher of the resin particles (for example, a temperature of 10 to 30 ° C. higher than the glass transition temperature of the resin particles). Are fused and united to form toner particles.

Through the above steps, toner particles are obtained.
In addition, after obtaining the aggregated particle dispersion liquid in which the aggregated particles are dispersed, the aggregated particle dispersion liquid and the resin particle dispersion liquid in which the resin particles are dispersed are further mixed, and the resin particles are further added to the surface of the aggregated particles. A process of aggregating to adhere to form second aggregated particles, and heating the second aggregated particle dispersion in which the second aggregated particles are dispersed to fuse and coalesce the second aggregated particles. The toner particles may be manufactured through a step of forming toner particles having a core / shell structure.

Here, after completion of the fusion / unification process, toner particles formed in the solution are dried through a known washing process, solid-liquid separation process, and drying process to obtain toner particles.
In the washing step, it is preferable to sufficiently carry out substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, etc. are preferably performed from the viewpoint of productivity. Also, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, or the like is preferably performed.

The toner according to the exemplary embodiment is produced, for example, by adding the above-described external additive containing the first silica particles and the second silica particles to the dry toner particles obtained and mixing them. The
Mixing is preferably performed by, for example, a V blender, a Henschel mixer, a Ladyge mixer, or the like.
Furthermore, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

[Mixing ratio of toner and carrier]
In the developer according to the exemplary embodiment, the mixing ratio (mass ratio) of the toner and the carrier is preferably toner: carrier = 1: 100 to 30: 100, and more preferably 3: 100 to 20: 100.

Here, if the following method is used, the volume average particle diameter of the oil-treated silica particles, which are the first silica particles and the second silica particles, and the oil release amount can be measured from the developer.
That is, in order to measure the volume average particle diameter of the oil-treated silica particles from the developer, the toner is separated from the developer by a known method, and the oil-treated silica particles in the toner (oil-treated silica externally added to the toner particles). 100 particles are observed with a scanning electron microscope (SEM) at a magnification of 40000 times, and the longest diameter and shortest diameter of each particle are measured by image analysis of the primary particles. taking measurement. The 50% diameter (D50v) in the cumulative frequency of the obtained sphere equivalent diameter is defined as the volume average particle diameter of the oil-treated silica particles.

Moreover, when measuring the oil release amount of the oil-treated silica particles from the developer, the following method is used.
That is, 2 g of a developer is added to 40 mL of an aqueous solution of 0.2% by mass of a surfactant (polyoxyethylene (10) octylphenyl ether having a polyoxyethylene polymerization degree of 10 manufactured by Wako Pure Chemical Industries, Ltd.) to disperse the toner. Disperse enough to do. In this state, an ultrasonic homogenizer US300T (manufactured by Nippon Seiki Seisakusho) is used, and ultrasonic vibration with an output of 20 W and a frequency of 20 kHz is applied for 1 minute to desorb the oil-treated silica particles. Then, it is treated at 3,000 rpm for 7 minutes in a 50 mL centrifuge with a sedimentation tube (compact cooling high-speed centrifuge Model M160 IV, manufactured by Sakuma Seisakusho) to separate toner particles, carrier dust, and other particles. The supernatant was removed with a membrane filter having a pore size of 5 μm (Nippon Polymere FHLP02500), and then applied to LC / MS / MS (Applied Biosystems Japan: 3200 Q TRAP (registered trademark) LC / MS / MS system). To determine the amount of oil released. Since the surface area ratio can be calculated from the particle size and the abundance ratio of the first and second silica particles (oil-treated silica particles) using the information obtained when measuring the volume average particle size, the amount of oil liberated is quantified. And the product of the surface area ratio calculated as the oil release amounts of the first and second silica particles, respectively.

<Image Forming Apparatus / Image Forming Method>
The image forming apparatus / image forming method according to the present embodiment will be described.
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic charge. Development means for containing an image developer and developing the electrostatic image formed on the surface of the image carrier as a toner image with the electrostatic image developer, and the toner image formed on the surface of the image carrier as a recording medium Transfer means for transferring to the surface of the recording medium, and fixing means for fixing the toner image transferred to the surface of the recording medium. The electrostatic charge image developer according to this embodiment is applied as the electrostatic charge image developer.

  In the image forming apparatus according to this embodiment, a charging process for charging the surface of the image carrier, an electrostatic charge image forming process for forming an electrostatic image on the surface of the charged image carrier, and an electrostatic charge according to this embodiment. A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with an image developer; a transfer step of transferring the toner image formed on the surface of the image carrier to the surface of the recording medium; An image forming method (an image forming method according to the present embodiment) including a fixing step of fixing the toner image transferred onto the surface of the recording medium is performed.

The image forming apparatus according to the present embodiment is a direct transfer type apparatus that directly transfers a toner image formed on the surface of an image carrier to a recording medium; the toner image formed on the surface of the image carrier is transferred to an intermediate transfer member An intermediate transfer type apparatus that primarily transfers the toner image transferred to the surface of the intermediate transfer body and then secondary transfer the toner image to the surface of the recording medium; after the toner image is transferred, the surface of the image carrier before charging is cleaned. An apparatus provided with a cleaning unit; a known image forming apparatus such as an apparatus provided with a charge removing unit that discharges the surface of an image holding member by irradiating a discharge light after charging a toner image and before charging is applied.
In the case of an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body on which a toner image is transferred to the surface, and a primary transfer that primarily transfers the toner image formed on the surface of the image holding body to the surface of the intermediate transfer body. And a secondary transfer unit that secondarily transfers the toner image transferred onto the surface of the intermediate transfer member onto the surface of the recording medium.

  In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, a process cartridge that accommodates the electrostatic charge image developer according to this embodiment and includes a developing unit is preferably used.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

FIG. 1 is a schematic configuration diagram illustrating an image forming apparatus according to the present embodiment.
The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a drive roll 22 and a support roll 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other in the left to right direction in the drawing. The vehicle travels in the direction toward the unit 10K. The support roll 24 is applied with a force in a direction away from the drive roll 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the support roll 24. An intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the drive roll 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The toner including the four color toners is supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. It should be noted that reference numerals with magenta (M), cyan (C), and black (K) are attached to the same parts as those of the first unit 10Y instead of yellow (Y). Description of the units 10M, 10C, and 10K will be omitted.

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, a charging roll (an example of a charging unit) 2Y for charging the surface of the photoreceptor 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on a color-separated image signal. Then, an exposure device (an example of an electrostatic image forming unit) 3 that forms an electrostatic image, and a developing device (an example of a developing unit) 4Y that develops the electrostatic image by supplying toner charged to the electrostatic image, developed A primary transfer roll 5Y (an example of a primary transfer unit) that transfers a toner image onto the intermediate transfer belt 20, and a photoconductor cleaning device (an example of a cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer. Are arranged in order.
The primary transfer roll 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rolls 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roll under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described.
First, prior to operation, the surface of the photoreceptor 1Y is charged to a potential of −600V to −800V by the charging roll 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (for example, volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (general resin resistance), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image having a yellow image pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photoreceptor 1Y is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) as a toner image by the developing device 4Y.

  In the developing device 4Y, for example, an electrostatic charge image developer containing at least yellow toner and a carrier is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged electric charge on the photoreceptor 1Y, and has a developer roll (a developer holding member). Example) is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a primary transfer bias is applied to the primary transfer roll 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roll 5Y is applied to the toner image, so that the photoreceptor is exposed. The toner image on 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time has a (+) polarity opposite to the polarity (−) of the toner, and is controlled to +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the photoreceptor cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rolls 5M, 5C, and 5K after the second unit 10M is also controlled in accordance with the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner. The

  The intermediate transfer belt 20 on which the four color toner images are transferred in multiple ways through the first to fourth units is disposed on the image transfer surface side of the intermediate transfer belt 20, the support roll 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roll (an example of a secondary transfer unit) 26 is formed to a secondary transfer portion configured. On the other hand, recording paper (an example of a recording medium) P is fed at a predetermined timing into a gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other via a supply mechanism, and the secondary transfer bias is supplied to the support roll. 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so The toner image is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by a resistance detection means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is fed into the pressure contact portions (nip portions) of a pair of fixing rolls in a fixing device (an example of a fixing unit) 28, and the toner image is fixed on the recording paper P to form a fixed image.

Examples of the recording paper P to which the toner image is transferred include plain paper used in electrophotographic copying machines, printers, and the like. In addition to the recording paper P, the recording medium may be an OHP sheet.
In order to further improve the smoothness of the image surface after fixing, the surface of the recording paper P is also preferably smooth. For example, coated paper whose surface of plain paper is coated with resin, art paper for printing, etc. are preferably used. Is done.

  The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.

<Process cartridge / toner cartridge>
The process cartridge according to this embodiment will be described.
The process cartridge according to the present embodiment accommodates the electrostatic image developer according to the present embodiment, and develops the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer. And a process cartridge that can be attached to and detached from the image forming apparatus.

  Note that the process cartridge according to the present embodiment is not limited to the above-described configuration, and other means such as a developing device and other units such as an image carrier, a charging unit, an electrostatic charge image forming unit, and a transfer unit, if necessary. And at least one selected from the above.

  Hereinafter, an example of the process cartridge according to the present embodiment will be shown, but the present invention is not limited to this. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

FIG. 2 is a schematic configuration diagram showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 2 is provided around the photoconductor 107 and the photoconductor 107 by, for example, a housing 117 provided with an attachment rail 116 and an opening 118 for exposure. A charging roller 108 (an example of a charging unit), a developing device 111 (an example of a developing unit), and a photoconductor cleaning device 113 (an example of a cleaning unit) are integrally combined and held to form a cartridge. Yes.
In FIG. 2, 109 is an exposure device (an example of an electrostatic charge image forming unit), 112 is a transfer device (an example of a transfer unit), 115 is a fixing device (an example of a fixing unit), and 300 is a recording paper (a recording medium). An example).

Next, the toner cartridge according to this embodiment will be described.
The toner cartridge according to the present exemplary embodiment is a toner cartridge that accommodates toner and is detachable from the image forming apparatus. The toner cartridge contains toner for replenishment to be supplied to the developing means provided in the image forming apparatus.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8C, and 8K are attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are each developing devices (colors). And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge becomes low, the toner cartridge is replaced.

  Hereinafter, although an Example and a comparative example are given and this embodiment is described in detail in detail, this embodiment is not limited to these Examples at all. Further, “part” means “part by mass” unless otherwise specified.

[Production of Oil-treated Silica Particles 1 (Volume Average Particle Size: 136 nm)]
After SiCl ₄ , hydrogen gas, and oxygen gas are mixed in the mixing chamber of the combustion burner, they are burned at a temperature of 1000 ° C. or higher and 3000 ° C. or lower. The silica base material was obtained by taking out silica powder from the gas after combustion. At this time, silica particles (1) having a volume average particle diameter of 136 nm were obtained by setting the molar ratio of hydrogen gas to oxygen gas to 1.3: 1.
100 parts of silica particles (1) and 500 parts of ethanol were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, after adding 10 parts of dimethyl silicone oil to 100 parts of silica particles and stirring for 15 minutes, 10 parts of dimethyl silicone oil (indicated as “Si oil” in Table 1) is further added to 100 parts of silica particles. The mixture was stirred for 15 minutes. Finally, the temperature was raised to 90 ° C. and ethanol was dried under reduced pressure. Thereafter, the treated product was taken out and further vacuum-dried at 120 ° C. for 30 minutes to obtain an oil treatment having a volume average particle size of 136 nm and a free oil amount of 10% by mass. Silica particles 1 were obtained.

[Production of Oil-treated Silica Particles 2 (Volume Average Particle Diameter: 180 nm)]
Oil-treated silica particles having a volume average particle size of 180 nm and a free oil amount of 10% by mass under the same conditions and method as the oil-treated silica particles 1 except that the molar ratio of hydrogen gas to oxygen gas is 1.2: 1. 2 was obtained.

[Preparation of oil-treated silica particles 3 (volume average particle size: 82 nm)]
Oil-treated silica particles having a volume average particle size of 82 nm and a free oil amount of 10% by mass under the same conditions and method as the oil-treated silica particles 1 except that the molar ratio of hydrogen gas to oxygen gas is 1.6: 1. 3 was obtained.

[Preparation of oil-treated silica particles 4 (volume average particle size: 136 nm)]
100 parts of silica particles (1) and 500 parts of ethanol used for the production of oil-treated silica particles 1 were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, 6 parts of dimethyl silicone oil was added to 100 parts of silica particles and stirred for 15 minutes. Finally, the temperature was raised to 90 ° C. and ethanol was dried under reduced pressure. Thereafter, the treated product was taken out and further vacuum-dried at 120 ° C. for 30 minutes to obtain oil-treated silica particles having a volume average particle size of 136 nm and a free oil amount of 3% by mass. 4 was obtained.

[Production of oil-treated silica particles 5 (volume average particle size: 136 nm)]
100 parts of silica particles (1) and 500 parts of ethanol used for the production of oil-treated silica particles 1 were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, after adding 10 parts of dimethyl silicone oil to 100 parts of silica particles and stirring for 15 minutes, 10 parts of dimethyl silicone oil was further added to 100 parts of silica particles and stirred for 15 minutes. Repeatedly, 30 parts dimethyl silicone oil is added to 100 parts total silica. Finally, the temperature was raised to 90 ° C. and ethanol was dried under reduced pressure. After that, the treated product was taken out and further vacuum-dried at 120 ° C. for 30 minutes to obtain an oil having a volume average particle size of 136 nm and a free oil amount of 20% by mass. Treated silica particles 5 were obtained.

[Preparation of oil-treated silica particles 6 (volume average particle diameter: 46 nm)]
Except for setting the molar ratio of hydrogen gas to oxygen gas to 2: 1, oil-treated silica particles 6 having a volume average particle size of 46 nm and a free oil amount of 10% by mass are obtained under the same conditions and method as those of oil-treated silica particles 1. Obtained.

[Preparation of oil-treated silica particles 7 (volume average particle diameter: 250 nm)]
Except that the molar ratio of hydrogen gas to oxygen gas is 1: 1, oil-treated silica particles 7 having a volume average particle size of 250 nm and a free oil amount of 10% by mass are obtained under the same conditions and method as those of oil-treated silica particles 1. Obtained.

[Preparation of Hydrophobized Silica Particles 8 (Volume Average Particle Size: 136 nm)]
100 parts of silica particles (1) and 500 parts of ethanol used for the production of oil-treated silica particles 1 were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, 20 parts of hexamethyldisilazane (indicated as “HMDS” in Table 1) was added to 100 parts of silica particles and stirred for 15 minutes. Finally, the temperature was raised to 90 ° C. and ethanol was dried under reduced pressure. After that, the treated product was taken out, further vacuum dried at 120 ° C. for 30 minutes, and treated with hexamethyldisilazane having a volume average particle size of 136 nm. Silica particles 8 were obtained.

[Preparation of oil-treated silica particles 9 (volume average particle size: 136 nm)]
100 parts of silica particles (1) and 500 parts of ethanol used for the production of oil-treated silica particles 1 were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, 3 parts of dimethyl silicone oil was added to 100 parts of silica particles and stirred for 15 minutes. Finally, the temperature was raised to 90 ° C. and ethanol was dried under reduced pressure. Thereafter, the treated product was taken out and further vacuum-dried at 120 ° C. for 30 minutes to obtain an oil treatment having a volume average particle size of 136 nm and a free oil amount of 1.5% by mass. Silica particles 9 were obtained.

[Production of Oil-treated Silica Particles 10 (Volume Average Particle Size: 136 nm)]
100 parts of silica particles (1) and 500 parts of ethanol used for the production of oil-treated silica particles 1 were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, after adding 10 parts of dimethyl silicone oil to 100 parts of silica particles and stirring for 15 minutes, 10 parts of dimethyl silicone oil was further added to 100 parts of silica particles and stirred for 15 minutes. Repeatedly, 40 parts dimethyl silicone oil is added to 100 parts total silica particles. Finally, the temperature was raised to 90 ° C. and ethanol was dried under reduced pressure. Thereafter, the treated product was taken out and further vacuum-dried at 120 ° C. for 30 minutes to obtain an oil having a volume average particle size of 136 nm and a free oil amount of 23% by mass. Treated silica particles 10 were obtained.

[Preparation of oil-treated silica particles a (volume average particle size: 35 nm)]
SiCl ₄ , hydrogen gas, and oxygen gas are mixed at a temperature of 1000 to 3000 ° C. after being mixed in the mixing chamber of the combustion burner. The silica base material was obtained by taking out silica powder from the gas after combustion. At this time, silica particles (a) having a particle diameter of 35 nm were obtained by setting the molar ratio of hydrogen gas to oxygen gas to 2.1: 1.
100 parts of silica particles (a) and 500 parts of ethanol were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, 10 parts of dimethyl silicone oil was added to 100 parts of silica particles and stirred for 15 minutes. Finally, the temperature was raised to 90 ° C. and ethanol was dried under reduced pressure. After that, the treated product was taken out and further vacuum-dried at 120 ° C. for 30 minutes, whereby an oil treatment with a volume average particle size of 35 nm and a free oil amount of 10% by mass Silica particles a were obtained.

[Production of Oil-treated Silica Particles b (Volume Average Particle Size: 13 nm)]
Oil-treated silica particles having a volume average particle size of 13 nm and a free oil amount of 10% by mass under the same conditions and method as the oil-treated silica particles a except that the molar ratio of hydrogen gas to oxygen gas is 2.3: 1. b was obtained.

[Preparation of oil-treated silica particles c (volume average particle diameter: 46 nm)]
Oil-treated silica particles c having a volume average particle size of 46 nm and a free oil amount of 10% by mass were obtained under the same conditions as the oil-treated silica particles a except that the molar ratio of hydrogen gas to oxygen gas was 2: 1. .

[Production of Oil-treated Silica Particles d (Volume Average Particle Size: 64 nm)]
Oil-treated silica particles having a volume average particle size of 64 nm and a free oil amount of 10% by mass under the same conditions and method as the oil-treated silica particles a except that the molar ratio of hydrogen gas to oxygen gas is 1.85: 1. d was obtained.

[Preparation of oil-treated silica particles e (volume average particle size: 8 nm)]
The oil-treated silica particles having a volume average particle size of 8 nm and a free oil amount of 10% by mass under the same conditions and method as the oil-treated silica particles a except that the molar ratio of hydrogen gas to oxygen gas is 2.4: 1. e was obtained.

[Preparation of Hydrophobized Silica Particles f (Volume Average Particle Size: 35 nm)]
100 parts of silica particles (a) used for preparation of the oil-treated silica particles a and 500 parts of ethanol were put in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, 20 parts of hexamethyldisilazane was added to 100 parts of silica particles and stirred for 15 minutes. Finally, the temperature was raised to 90 ° C., and ethanol was dried under reduced pressure. Then, the treated product was taken out, further vacuum dried at 120 ° C. for 30 minutes, and treated with hexamethyldisilazane having a volume average particle size of 35 nm. Silica particles f were obtained.

[Preparation of core material A (electrical resistance: 2.5 × 10 ^8.5 Ωcm)]
1318 parts by weight of Fe ₂ O ₃ , 586 parts by weight of Mn (OH) _{2 and} 96 parts by weight of Mg (OH) ₂ were mixed, a dispersant, water and zirconia beads having a media diameter of 1 mm were added, and pulverized and mixed with a sand mill. . After filtering and drying the zirconia beads, a mixed oxide was obtained using a rotary kiln at 20 rpm and 900 ° C. Next, a dispersant and water were added, and 6.6 parts by weight of polyvinyl alcohol was further added, and the mixture was pulverized and mixed with a wet ball mill for 5 hours. Next, it was granulated and dried so as to have a dry particle size of 40 μm with a spray dryer. Furthermore, baking was performed in an electric furnace in an oxygen-nitrogen mixed atmosphere at a temperature of 1100 ° C. and an oxygen concentration of 1% for 5 hours. The obtained particles are subjected to a crushing step and a classification step, then heated in a rotary kiln at 15 rpm and 1000 ° C. for 1 hour, and after a classification step again, a core material having an electric resistance of 2.5 × 10 ^8.5 Ωcm. A was obtained.

[Production of Core Material B (Electric Resistance: 8.2 × 10 ^9.5 Ωcm)]
After passing through the crushing step and the classification step, the electrical resistance is 8.2 × 10 with the same conditions and method as in the core A except that the rotary kiln is heated at 15 rpm and 1000 ° C. for 2 hours and the classification step is repeated. A core material B of ^9.5 Ωcm was obtained.

[Production of Core Material C (Electrical Resistance: 5.6 × 10 ^7.2 Ωcm)]
After passing through the crushing step and the classification step, the electrical resistance is 5.6 × 10 with the same conditions and method as in the core A except that the rotary kiln is heated at 15 rpm and 900 ° C. for 2 hours and the classification step is performed again. A core material C of ^7.2 Ωcm was obtained.

[Production of Core Material D (Electric Resistance: 3.8 × 10 ^6.8 Ωcm)]
After passing through the crushing step and the classifying step, the electric resistance is 3.8 × 10 with the same conditions and method as in the core A except that the rotary kiln is heated for 1 hour at 15 rpm and 800 ° C. A core material D of ^6.8 Ωcm was obtained.

[Production of Core Material E (Electric Resistance: 6.7 × 10 ^10.5 Ωcm)]
After passing through the crushing step and the classification step, the electric resistance is 6.7 × 10 with the same conditions and method as in the core A except that the rotary kiln is heated at 15 rpm and 1100 ° C. for 2 hours and the classification step is repeated. A core material E of ^10.5 Ωcm was obtained.

[Production of toner particles]
-Preparation of polyester resin dispersion-
・ Ethylene glycol [Wako Pure Chemical Industries, Ltd.] 37 parts ・ Neopentyl glycol [Wako Pure Chemical Industries, Ltd.] 65 parts ・ 1,9 Nonanediol [Wako Pure Chemical Industries, Ltd.] 32 parts ・96 parts of terephthalic acid [manufactured by Wako Pure Chemical Industries, Ltd.] The above monomer was charged into a flask, and the temperature was raised to 200 ° C. over 1 hour. After confirming that the reaction system was stirred, dibutyltin oxide was added. 1.2 parts were added. Further, while distilling off the generated water, the temperature was increased from the same temperature to 240 ° C. over 6 hours, and the dehydration condensation reaction was continued at 240 ° C. for another 4 hours. The acid value was 9.4 mgKOH / g, and the weight average molecular weight. A polyester resin A having a glass transition temperature of 13,000 and 62 ° C. was obtained.

Subsequently, the polyester resin A was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 parts per minute. A 0.37% diluted aqueous ammonia solution obtained by diluting reagent ammonia water with ion-exchanged water is put into a separately prepared aqueous medium tank, and the polyester is heated at 120 ° C. with a heat exchanger at a rate of 0.1 liter per minute. Simultaneously with the resin melt, it was transferred to the Cavitron. The Cavitron is operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² .
An amorphous polyester resin dispersion in which resin particles having a volume average particle size of 160 nm, a solid content of 30%, a glass transition temperature of 62 ° C., and a weight average molecular weight Mw of 13,000 was obtained was obtained.

-Preparation of colorant dispersion-
-Cyan pigment (Pigment Blue 15: 3, manufactured by Dainichi Seika Kogyo Co., Ltd.) 10 parts-Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts-Ion-exchanged water 80 parts The mixture was mixed and dispersed for 1 hour with a high-pressure impact type disperser [HJP30006, manufactured by Sugino Machine Co., Ltd.] to obtain a colorant dispersion having a volume average particle size of 180 nm and a solid content of 20%.

-Preparation of release agent dispersion-
-Paraffin wax (HNP 9, manufactured by Nippon Seiki Co., Ltd.) 50 parts-Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts-Ion-exchanged water 200 parts After sufficiently mixing and dispersing with Ultra Turrax T50, a release agent dispersion having a volume average particle size of 200 nm and a solid content of 20% was obtained.

-Production of toner particles 1-
・ Polyester resin dispersion 200 parts ・ Colorant dispersion 25 parts ・ Polyaluminum chloride 0.4 parts ・ Ion-exchanged water 100 parts The above ingredients are put into a stainless steel flask and fully used with IKA Ultra Turrax. After mixing and dispersing, the flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 30 minutes, 70 parts of the same polyester resin dispersion as above was gently added thereto.

Then, after adjusting the pH of the system to 8.0 using a 0.5 mol / L sodium hydroxide aqueous solution, the stainless steel flask was sealed, and the stirring shaft seal was magnetically sealed while stirring was continued. Heat to 90 ° C. and hold for 3 hours. After completion of the reaction, the temperature lowering rate was cooled at 2 ° C./min, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed with 3 L of ion exchange water at 30 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 6 times. When the pH of the filtrate became 7.54 and the electric conductivity was 6.5 μS / cm, No. 2 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain toner particles.
The volume average particle diameter D50v of the toner particles (1) was measured with a Coulter counter. As a result, it was 5.8 μm and SF1 was 130.

[Examples 1-9, Comparative Examples 1-8]
According to the combinations shown in Table 1, 2.0 parts by mass of silica particles (1) and 1.0 part by mass of silica particles (2) as external additives are added to 20 parts by mass of toner particles, and a Henschel mixer is used. Each toner (toner (1) to (9), (C1) to (C8)) was obtained by mixing at 2000 rpm for 3 minutes.

  Then, each toner obtained and the carrier prepared by the following method are put in a V blender at a ratio of toner: carrier = 5: 95 (mass ratio) according to the combination of Table 1, and stirred for 20 minutes for development. An agent was obtained.

In addition, as a carrier, what was produced as follows using the core materials AE obtained as mentioned above was used.
1,000 parts of a core material is put into a kneader, and a perfluorooctylmethyl acrylate-methyl methacrylate copolymer (polymerization ratio: 20/80, Tg: 72 ° C., weight average molecular weight: 72,000, Soken Chemical Co., Ltd.) [Product] A solution of 150 parts in 700 parts of toluene was added, mixed at room temperature for 20 minutes, heated to 70 ° C. and dried under reduced pressure, then taken out to obtain a coated carrier. The carrier was obtained by sieving with a mesh having an opening of 75 μm to remove coarse powder, and the carrier shape factor SF1 was 122.

[Evaluation]
The developer obtained in each example was evaluated for fog and image density. The results are shown in Table 1.

-Evaluation of fog and image density-
The fog was evaluated as follows.
The resulting developer was left for 3 days under high temperature and high humidity (28 ° C., 85% RH).
Thereafter, a 700 Digital Color Press (manufactured by Fuji Xerox Co., Ltd.) in which a developer was filled in the developer was used to prepare a patch of 100 cm solid and 5 cm × 5 cm on C2 paper manufactured by Fuji Xerox Co., Ltd.
The density of this patch was measured, and this was designated as density 1. Here, this density was measured with an image densitometer X-Rite 938 (manufactured by X-Rite).
Next, 100,000 images with an area coverage of 40% were output. The environment at this time was 28 ° C. and 85% RH. The density of the output background portion of the 100,000th sheet was measured in the same manner as the density 1, and also visually confirmed. The measured density was defined as the fog density at the time of outputting a high image density image.
Subsequently, after leaving the apparatus under high temperature and high humidity (28 ° C., 85% RH) for 3 days, 100,000 images with an image density of 1% were output. The environment at the time of output was 28 ° C. and 85% RH. Here, the density of the output background portion of the first sheet was measured in the same manner as the density 1, and visual confirmation was also performed. The measured density (fog density) was defined as the fog density after standing.
Thereafter, a patch of 100 cm solid and 5 cm × 5 cm was prepared, and the density of this patch was measured in the same manner as density 1 and this was set to density 2.

Based on the two fog densities obtained as described above and visual observation, evaluation was performed based on the following evaluation criteria. The allowable range up to G3 was set.
-Evaluation criteria for fogging-
G1: The fog density is less than 0.2, and partial fogging is not seen visually.
G2: The fog density is less than 0.2, but slight fog is visually observed.
G3: The fog density is less than 0.2, but partial fog is visually observed.
G4: The fog density is less than 0.2, but overall fog is visible.
G5: The fog density is 0.2 or more.

Further, the difference between the concentration 2 and the concentration 1 obtained as described above was obtained, and this was taken as the Δ concentration. That is, Δ concentration = concentration 2−concentration 1. The allowable range up to G3 was set.
-Evaluation criteria for concentration reduction-
G1: 0 <Δ concentration ≦ 0.1
G2: 0.1 <Δ concentration ≦ 0.2
G3: 0.2 <Δ concentration ≦ 0.3
G4: 0.3 <Δ concentration ≦ 0.4
G5: 0.4 <Δ concentration

  From the above results, in this embodiment, compared to the comparative example, fog caused by poor toner mixing at the time of outputting a high image density, fog caused by charge leakage after being left, and low image density image It can be seen that good results were obtained in all the evaluations of the decrease in image density when the image was continuously output.

1Y, 1M, 1C, 1K photoconductor (an example of an image carrier)
2Y, 2M, 2C, 2K charging roll (an example of charging means)
3. Exposure device (an example of electrostatic charge image forming means)
3Y, 3M, 3C, 3K Laser beams 4Y, 4M, 4C, 4K Developing device (an example of developing means)
5Y, 5M, 5C, 5K primary transfer roll (an example of primary transfer means)
6Y, 6M, 6C, 6K Photoconductor cleaning device (an example of cleaning means)
8Y, 8M, 8C, 8K Toner cartridge 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt (an example of an intermediate transfer member)
22 Drive roll 24 Support roll 26 Secondary transfer roll (an example of secondary transfer means)
30 Intermediate transfer member cleaning device 107 Photosensitive member (an example of an image holding member)
108 Charging roll (an example of charging means)
109 Exposure apparatus (an example of electrostatic charge image forming means)
111 Developing device (an example of developing means)
112 Transfer device (an example of transfer means)
113 photoconductor cleaning device (an example of cleaning means)
115 Fixing device (an example of fixing means)
116 Attachment rail 118 Opening 117 for exposure 117 Case 200 Process cartridge 300 Recording paper (an example of recording medium)
P Recording paper (an example of a recording medium)

Claims (5)

A core material having an electric resistance of 1 × 10 ⁷ Ωcm or more and 1 × 10 ¹⁰ Ωcm or less under an electric field of 4800 V / cm at 30 ° C. and 85% RH, and a coating layer containing a resin provided on the surface of the core material; A carrier having
Toner particles, a first silica particle having a volume average particle size of 70 nm to 200 nm that has been surface treated with oil, and a second silica particle having a volume average particle size of 10 nm to 50 nm that has been surface treated with oil A toner having an external additive,
An electrostatic charge image developer.   The electrostatic charge image developer according to claim 1, wherein an oil liberation amount in the first silica particles in the toner is 3% by mass or more and 20% by mass or less.   The electrostatic charge image developer according to claim 1, wherein the toner particles in the toner are toner particles produced by a wet process. The electrostatic image developer according to claim 1 is contained, and the electrostatic image formed on the surface of the image carrier is developed as a toner image by the electrostatic image developer. With developing means,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
An electrostatic image developer according to any one of claims 1 to 3 is accommodated, and the electrostatic image formed on the surface of the image carrier is developed as a toner image by the electrostatic image developer. Developing means,
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: