WO2016117344A1

WO2016117344A1 - Silicone oil-treated silica particles and toner for electrophotography

Info

Publication number: WO2016117344A1
Application number: PCT/JP2016/000308
Authority: WO
Inventors: 友也山野; 中村　正博; 胆治小松原
Original assignee: 株式会社トクヤマ
Priority date: 2015-01-23
Filing date: 2016-01-21
Publication date: 2016-07-28

Abstract

Silicone oil-treated silica particles are provided with a silica particle body and silicone oil. The BET specific surface of the silica particle body is 70-120 m²/g. The silica particle body is surface-treated with silicone oil. The amount of free silicone oil that is separated from the surface of the silica particle body among the silicone oil is 2.0-5.0 mass% with respect to the silica particle body. The degree of agglomeration of surface-treated styrene-acrylic resin particles in which 2 parts by mass of silicone oil-treated silica particles are mixed with 100 parts by mass of styrene-acrylic resin particles having a median particle size value of 5-8 µm is 18% or less.

Description

Silicone oil-treated silica particles and electrophotographic toner

The present disclosure relates to a silicone oil-treated silica particle and an electrophotographic toner including the same, and more particularly to a silicone oil-treated silica particle including a silica particle body and silicone oil and an electrophotographic toner including the same.

External additives are widely used for toners used as developers in electrophotographic technologies such as copying machines and laser printers for the purpose of imparting fluidity, improving charging efficiency, and controlling the amount of charge. As such an external additive, silica is generally used.

In recent years, copiers and printers have become more and more demanding of higher speed, smaller equipment, color, and higher image quality, and the toner design used also meets such demands. Development is underway.

Especially in electrophotographic technology, maintaining stable image characteristics over a long period is an essential issue. Therefore, various studies have been made on silica, which is an external additive for toner. (For example, Patent Documents 1, 2, and 3)

In silica, primary particles with a diameter of several to several tens of nanometers are chemically bonded and aggregated to form primary aggregated particles, and the primary aggregated particles are physically aggregated to aggregate with a diameter of several tens to several hundreds of μm. It exists as particles. The role of silica in the toner is mainly to impart fluidity and stabilize charging characteristics. In order to fulfill this role, surface treatment is an important point as well as the size and properties of the aggregated particles of silica. Patent Documents 1 to 3 disclose silica that has been treated with silicone oil as a surface treatment.

JP 2009-98700 A JP 2014-174475 A JP 2014-174501 A

However, when the printing speed of copiers and printers is increased or when high resolution is studied, conventional toner using silica as an additive causes aggregation, resulting in printing defects called color loss and density unevenness. It became clear that the problem occurred.

The present disclosure has been made in view of such a point, and the object of the present disclosure is to provide a silicone oil-treated silica as an external additive for toner that improves color quality by reducing color loss and density unevenness during printing. To provide particles.

One aspect of the silicone oil-treated silica particles of the present disclosure is a silicone oil-treated silica particle including a silica particle body and a silicone oil, wherein the silica particle body has a BET specific surface area of 70 m ² / g or more and 120 m ² / g, the silica particle main body is surface-treated with the silicone oil, and the amount of free silicone oil released from the surface of the silica particle main body in the silicone oil is 2 with respect to the silica particle main body. A surface obtained by mixing 2 parts by mass of the silicone oil-treated silica particles with respect to 100 parts by mass of the styrene acrylic resin particles having a particle diameter of from 0 to 5.0% by mass and a median particle diameter of 5 to 8 μm. The degree of aggregation of the treated styrene acrylic resin particles is 18% or less. Here, the styrene acrylic resin is a resin obtained by copolymerizing styrene and acrylic acid or an alkyl acrylate ester.

The maximum value αmax of the fractal shape parameter α values in the measurement ranges of 20 to 30 nm, 30 to 40 nm, and 50 to 70 nm of the silica particle body is preferably 2.9 or more.

It is preferable that the particle density of the silica particle body measured by the He gas pycnometer method is 2.23 g / cm ³ or more.

The apparent density of the silica particle main body is preferably 20 g / l or more and 35 g / l or less.

The electrophotographic toner of the present disclosure contains the silicone oil-treated silica particles as an external additive.

The method for producing the silicone oil-treated silica particles of the present disclosure includes a step of preparing a silica particle body having a BET specific surface area of 70 m ² / g or more and 120 m ² / g or less, adding silicone oil to the silica particle body, And a step of coating the surface of the silica particle body with silicone oil to obtain the above-mentioned silicone oil-treated silica particles.

When the silicone oil-treated silica particles of the present disclosure are used as an external additive for toner for electrophotography, the toner fluidity is improved and the toner is prevented from aggregating. Unevenness is reduced.

Hereinafter, embodiments of the present disclosure will be described in detail based on the drawings. The following description of the preferred embodiments is merely exemplary in nature and is not intended to limit the present disclosure, its application, or its application. In the following drawings, components having substantially the same function are denoted by the same reference numerals for the sake of brevity.

(Embodiment)
The silicone oil-treated silica particles according to the embodiment are obtained by surface-treating a silica particle body with silicone oil. Hereinafter, the silica particle body before surface treatment with silicone oil is simply referred to as silica particles, and the surface treated with silicone oil is referred to as silicone oil-treated silica particles.

The silicone oil-treated silica particles of the present embodiment can be used as an external additive for toners and powder paints, and as a filler for various resin materials such as epoxy resins and acrylic resins. Among these, since it is excellent in dispersibility and imparts good fluidity, it can be particularly suitably used as an external additive for an electrophotographic toner.

In the toner for electrophotography, the silica particles treated with silicone oil are added as external additives to resin particles made of styrene acrylic resin or polyester resin as a toner raw material, and are stirred and mixed to adhere to the surface of the resin particles. At this time, it is known that when the silicone oil-treated silica particles are dispersed and adhered to the resin particle surface to sub-micron aggregated particles, the fluidity and charging characteristics of the toner are improved. However, when the printing conditions of electrophotography become more severe, the conventional toner becomes insufficient in print quality. As a result of various studies conducted by the inventors of the present application in order to solve the problem, the technique of the present disclosure is applied. It has come. The contents are the particle size of the silica particles (specified by the BET specific surface area), the amount of free silicone oil in the silicone oil-treated silica particles surface-treated with silicone oil, and the toner added with the silicone oil-treated silica particles (pseudo toner). It means that the print quality is improved when the degree of aggregation of (alternative) is in a predetermined relationship, and that the fractal shape parameter, particle density and apparent density of the silica particles are also preferably in a predetermined relationship. is there. This will be specifically described below.

The silica particles as the base material are preferably dry silica because of their low water content. Dry silica is produced by supplying a silicon compound into a flame. Such silica particles have little moisture and coarse particles, and when used as an external additive, the effect of imparting fluidity to the toner resin and charging Excellent in imparting sex. In particular, silica particles produced by flame pyrolysis of chlorosilane, generally called fumed silica, are preferred.

An example of a suitable production method for the above-mentioned dry silica is the production method described in JP-A-2008-19157. That is, a burner having a multi-tube structure having a central tube and a first annular tube formed on the outer periphery thereof is used, a mixed gas containing a siloxane compound gas and oxygen gas is supplied to the central tube of the burner, and hydrogen A method for producing dry silica particles by supplying an auxiliary gas containing a gas or a hydrocarbon gas as a combustible component to the first annular tube of the burner and performing combustion is exemplified. Moreover, the method of manufacturing by the flame thermal decomposition of chlorosilane generally called fumed silica is also mentioned.

In the present embodiment, the BET specific surface area of the silica particles is 70 m ² / g or more and 120 m ² / g or less. When the BET specific surface area is less than 70 m ² / g, the particle size of the silica particles becomes too large and is easily detached from the surface of the toner, which may reduce the fluidity and the spacer imparting effect as functions of the external additive. is there. On the other hand, if the BET specific surface area is larger than 120 m ² / g, the particle diameter becomes too small, and the spacer imparting effect may be lowered. Further, when it is 80 m ² / g or more and 90 m ² / g or less, the fluidity of the toner and the effect of imparting the spacer become better when used as an external additive of the toner. The BET specific surface area of the silica particles varies depending on the production method and production conditions of the silica particles.

The silica particles according to the present embodiment preferably have a fractal shape parameter αmax of 2.9 or more when the lower limit of the measurement range is 20 nm or more. The fractal shape parameter is a “fractal shape parameter (α value) serving as an index of particle shape” corresponding to the frequency of periodic structures of various sizes. W. Schaefer et al., Physical Review Letters, Volume 52, Number 26, p. 2371-p. 2374 (1984). The content of the paper is incorporated as part of the description of the present application.

That is, the α value can be determined by small-angle X-ray scattering measurement. According to the small-angle X-ray scattering measurement, it is possible to obtain information on the periodic structure of nanometers or more that cannot be obtained by ordinary X-ray diffraction (information on the period and frequency of the structure), and the α value is determined based on this information. To do.

Specifically, the fractal shape parameter α value is measured by the following method. That is, since there is a relationship of the following formula (2) between the scattering intensity (I) after the background correction in small-angle X-ray scattering, the scattering vector (k), and the fractal shape parameter (α), the horizontal axis is represented by k. The α value can be determined from a small angle X-ray scattering curve plotted with the vertical axis as I.

I∝k ^-α Formula (1)
Where k = 4πλ ⁻¹ sin θ
In the formula, I: scattering intensity k: scattering vector (unit: nm ⁻¹ )
π: Circumference ratio λ: Incident X-ray wavelength (unit: nm)
θ: X-ray scattering angle (θ is a value obtained by multiplying the scanning angle of the detector by 0.5)

In order to obtain a small-angle X-ray scattering curve, first, monochromatic X-rays are applied to a narrow aperture sample using slits and blocks, and the X-rays scattered by the sample are changed while changing the scanning angle of the detector. To detect. Then, a relationship is obtained by plotting the scattering vector (k) obtained from the X-ray scattering angle (θ) by the above formula on the horizontal axis and the scattering intensity (I) corrected for the background on the vertical axis. If plotting on a logarithmic scale at this time, the slope of the tangent of the small-angle X-ray scattering curve at a certain k value becomes equal to -α, so that the α value can be obtained.

Note that the background correction can be performed by subtracting the scattering intensity of only the measurement cell without the sample from the scattering intensity of the sample. Here, if the size of the α value analysis target is D (nm), there is a relationship of Bragg's equation (2D × sin θ = λ) between D, the X-ray scattering angle θ, and the incident X-ray wavelength λ. Therefore, the relationship of the following formula is established between k and D.

D = 2πk ⁻¹

Here, when such small-angle X-ray scattering is measured for silica particles, the frequency of the periodic structure of each size in the primary particle and its aggregated particle structure is analyzed by analyzing the obtained small-angle X-ray scattering curve. The α value corresponding to can be obtained. In this measurement, the α value varies depending on the measurement range (range), and the α value increases as the range decreases. Therefore, the measurement ranges are set to 20 to 30 nm, 30 to 50 nm, and 50 to 70 nm, the α value of each measurement range is calculated, and the maximum value is determined as the αmax value. In this embodiment, the BET specific surface area of the silica particles is 70 m ² / g or more and 120 m ² / g or less, and the particle size of the primary particles is about 18 to 26 nm. Accordingly, in the measurement range smaller than 20 nm, a part of the particle surface of the primary particle is measured, and the α value becomes large. In this embodiment, since the silica particles are in the form of primary particles or aggregated particles when used as an additive, the measurement range is set to the above range. In the case of silica particles having a BET specific surface area in the above range, the α value gradually decreases and cannot have a maximum value in the measurement exceeding 70 nm.

By the way, it is known that when the α value approaches 4 and becomes larger, the structure becomes smaller and becomes closer to a true sphere. Therefore, it can be said that the larger the α value in the primary particles and the aggregated particle structure, the better the dispersibility of the silica particles. Therefore, when the αmax value is smaller than 2.9, the dispersibility of the silica particles is inferior, and when used as a toner external additive, silica aggregates and toner aggregates are likely to be formed, and the color density during printing is reduced. There is a risk of deterioration and color loss. The αmax value is preferably 3.0 or more, and more preferably 3.1 or more. The upper limit of the αmax value is not particularly limited and is preferably close to 4, but is more preferably 3.8 or less for practical use.

In the present embodiment, the particle density of the silica particles measured by the He gas pycnometer method is preferably 2.23 g / cm ³ or more. When the particle density of the silica particles is smaller than 2.23 g / cm ³ , the surface of the photoconductor is scratched because the elastic deformation is large when the silica particles are pressed against the photoconductor in the electrophotographic printing process. there is a possibility. As a result, filming occurs, and there is a risk that color density may be lowered or color loss may occur during printing. When the particle density of the silica particles is 2.24 g / cm ³ or more, there is almost no risk of color density reduction or color loss during printing, which is more preferable.

The apparent density of the silica particles according to the present embodiment is preferably 20 g / l or more and 35 g / l or less. Furthermore, it is more preferably 21 g / l or more and 30 g / l or less, and particularly preferably 21 g / l or more and 27 g / l or less. The apparent density is measured according to JIS 5101-12-1 Pigment Test Method. When the apparent density is less than 20 g / l, it is difficult to uniformly treat the surface with silicone oil, and the degree of surface treatment may vary. Specifically, if the coating amount of the silicone oil on the surface of the silica particles varies depending on the place in the treatment batch, the silicone oil-treated silica is used when the silicone oil-treated silica particles are used as an external additive for the toner. This may cause a poor dispersion of particles or a toner aggregate, and may cause a decrease in color density or color loss during printing. On the other hand, if the apparent density is higher than 35 g / l, the silicone oil treatment is performed in a state where the silica particles are aggregated, and if added to the toner, toner aggregates may be formed. This may cause a drop or color loss. The apparent density can be adjusted using a known method without limitation. Specifically, when the apparent density is smaller than the above range, compression is performed using a degassing press or the like, and the apparent density may be adjusted to be within the above range.

The silica particles according to this embodiment are surface-treated with silicone oil to form silicone oil-treated silica particles. The silicone oil used in the present embodiment is not particularly limited, and any known one can be used without limitation. Specifically, dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, amino modified silicone oil, epoxy modified silicone oil, carboxy modified silicone oil, carbinol modified silicone oil, polyether modified silicone oil, alkyl modified silicone Examples thereof include oil and fluorine-modified silicone oil.

The viscosity of the silicone oil is not particularly limited, but a viscosity of 20 to 500 cSt can be preferably used. When the viscosity of the silicone oil is small beyond this range, the silicone oil becomes volatile, so that it tends to be difficult to adhere a predetermined amount to the surface of the silica particles. It tends to be non-uniform. Further, two or more types of silicone oils having different functional groups may be mixed and used, or two or more types of silicone oils having the same functional group and different viscosity and molecular weight distribution may be used in combination.

The surface treatment method using silicone oil is not particularly limited. As a treatment method, by dissolving silicone oil in a solvent such as toluene, dispersing silica particles in the solution, evaporating the solvent to attach silicone oil to the surface of the silica particles, and further performing a predetermined heat treatment Method (wet treatment method) and method (dry treatment) by spraying silicone oil onto silica particles while mixing in a mixer or fluidized bed, adhering silicone oil to the silica particle surface, and performing a predetermined heat treatment Law).

Among the above wet processing methods and dry processing methods, the reason why silica particles processed more uniformly are obtained, and because no organic solvent is used, the dry processing method is selected because it is excellent in terms of cost, safety, and environment. It is preferable to use it.

In the dry treatment method, spraying the silicone oil in a good mixed state is important for uniform silicone oil treatment. As a method of mixing the silica fine powder, a mixer is preferable. Mixing by a mixer has a higher collision frequency between silica particles compared to mixing by a fluidized bed, and silicone oil is frequently exchanged between silica particles, so that surface-treated silica particles processed more uniformly can be obtained. It tends to be.

In the stirring in the mixer in the silicone oil treatment, it is preferable to select the rotation speed of stirring and the shape of the stirring blade so that the silica particles are fluidized and a stable stirring state is obtained. The container may or may not be sealed.

In this embodiment, when the silicone oil treatment is performed by the dry treatment method, the spray particle size when spraying the silicone oil is preferably 80 μm or less. By setting the spray particle size within this range, it is easy to perform uniform processing. As a spraying device for silicone oil, a one-fluid nozzle, a two-fluid nozzle, or the like can be used. It is preferable to use a two-fluid nozzle because it is possible to spray with a smaller particle size.

In the present embodiment, it is preferable that the silicone oil treatment is performed with a predetermined heat treatment after the silicone oil is adhered to the surface of the silica particles. The heat treatment is not particularly limited, but can be preferably performed in an environment of 100 ° C. to 300 ° C.

Silicone oil in silica oil-treated silica particles is divided into those bonded to silica particles and those that are simply attached to the surface by physical adsorption. The silicone oil bonded to the silica particles has a silanol group on the surface of the silica particles and is immobilized by weak chemical bonds such as hydrogen bonds. Further, the silicone oil simply adhering to the surface can be released from the silicone oil-treated silica particles by a hydrocarbon-based organic solvent such as hexane. Silicone oil that can be liberated from the silicone oil-treated silica particles by an organic solvent is called free silicone oil.

The amount of free silicone oil can be determined by immersing the silicone oil-treated silica particles in normal hexane and measuring the amount of silicone oil eluted. Specifically, it can be calculated by the following method. Specifically, first, 0.5 g of sample silicone oil-treated silica particles and 32 ml of normal hexane are placed in a centrifuge tube having a capacity of 50 ml, and subjected to ultrasonic waves for 30 minutes using an ultrasonic cleaner (for example, an ultrasonic cleaner 1510JMTH manufactured by Yamato Kagaku). Wash and suspend. The resulting suspension is centrifuged to separate and recover the solid phase (silica). To the recovered silica, 32 ml of normal hexane was further added, and the operations of ultrasonic cleaning and centrifugation were repeated three times in total to separate and recover the solid phase (silica), followed by drying under reduced pressure (120 ° C., 12 hours) to obtain a dry powder. obtain. The carbon content of this powder is measured using a total nitrogen / total carbon measuring device (for example, Sumigraph NC-22F manufactured by Sumika Chemical Analysis Co., Ltd.) using an oxygen circulating combustion method. The total carbon content in 0.5 g of the sample is measured in advance, and the amount of the extracted free silicone oil is calculated from the difference from the total carbon content. Specifically, the carbon content corresponding to the above difference is converted into the amount of silicone oil (structure formula: — (Si (CH ₃ ) ₂ —O) _n —) having dimethylsiloxane as the main chain, and the amount of free silicone oil Just do it.

The amount of the free silicone oil is 2.0% by mass or more and 5.0% by mass or less, and preferably 2.0% by mass or more and 4.0% by mass or less with respect to the silica particle body. If the amount of free silicone oil is less than 2.0% by mass, the amount of triboelectric charge between the toner and the carrier varies depending on the location when the silicone oil-treated silica particles are used as an external additive for the toner. In this case, there is a high possibility that a decrease in color density or color loss will occur. On the other hand, when the amount of the free silicone oil is more than 5.0% by mass, there is a possibility that excessive free silicone oil may aggregate the toner when the silicone oil-treated silica particles are used as an external additive of the toner. There is a risk that the color density decreases and color loss occurs during printing. The amount of free silicone oil varies depending on the conditions when the silica particles are surface treated with silicone oil.

In this embodiment, the median particle diameter is 5 to 8 μm, the glass transition temperature is 58 to 63 ° C., the melt flow rate is 2.2 to 5.0 g / 10 min (150 ° C., 21.1 N), and the weight average The degree of aggregation of the surface-treated styrene acrylic resin particles obtained by mixing 2 parts by mass of silicone oil-treated silica particles with 100 parts by mass of styrene acrylic resin particles having a molecular weight of 220,000 to 280,000 is 18% or less, 15 % Or less, and more preferably 13% or less. The glass transition temperature is 58.6 to 62.4 ° C., the melt flow rate is 2.5 to 4.7 g / 10 min (150 ° C., 21.1 N), and the weight average molecular weight is 230,000 to 270,000. It is preferable. The median particle diameter is the median diameter (median diameter) of the volume distribution measured with a particle size distribution meter. Specific examples of the styrene acrylic resin particles having the above physical properties include Hymer SB-317 manufactured by Sanyo Chemical Industries. Here, the styrene acrylic resin particles are pseudo toners. The degree of aggregation is measured using a powder tester. If the degree of aggregation is more than 18%, the amount of toner aggregates increases, so that the risk of color density reduction and color loss during printing increases. Accordingly, the smaller the degree of aggregation, the better. However, in the case of silicone oil-treated silica particles using a silica particle body having a BET specific surface area of 70 m ² / g or more and 120 m ² / g or less, it is usually 5% or more. It is. In general, when the surface treatment is performed using the same surface treating agent, the degree of aggregation tends to decrease as the BET specific surface area of the silica particle body increases. Further, when the amount of free silicone oil is large or the apparent density of the silica particle body is small, the degree of aggregation tends to increase.

Hereinafter, a method for producing the silicone oil-treated silica particles of this embodiment will be described. Silicone oil is added to the aforementioned silica particles to coat the surface. As the silicone oil used in the present embodiment, those described above can be preferably used.

In the present embodiment, the amount of silicone oil added may be an amount that can impart sufficient hydrophobicity to the particle surface, and the amount of free silicone oil in the resulting silicone oil-treated silica particles falls within the above range. For example, when the amount of the free silicone oil is 2.0% by mass or more and 5.0% by mass or less with respect to the silica particle body, about 6 to 18% by mass, 2.0% by mass per mass of the silica particle body. When the content is 4.0 mass% or less, about 6 to 15 mass% may be added per mass of the silica particle body. Since it differs depending on the type of silicone oil used and the specific surface area of the silica particles, it cannot be said unconditionally. For example, if the specific surface area of the silica particles of the base material is 100 m ² / g, 100 mass of silica of the base material 8 to 16 parts by weight, more preferably 10 to 14 parts by weight, and a specific surface area of 70 m ² / g, 6 to 14 parts by weight, more preferably 8 to 12 parts by weight with respect to 100 parts by weight of silica. It is preferable to add part by mass.

The silicone oil coating method is not particularly limited as long as the surface of the silica particle main body can be coated with silicone oil, and as a treatment method, the silicone oil is dissolved in a solvent such as toluene, and the silica particles are dissolved in the solution. A method in which silicone oil is adhered to the surface of the silica particles by dispersing and evaporating the solvent, followed by a predetermined heat treatment (wet treatment method), and mixing with the silica particles while mixing in a mixer or fluidized bed A method (dry treatment method) by spraying silicone oil, adhering silicone oil to the surface of silica particles, and performing a predetermined heat treatment.

In the present invention, the silicone oil treatment is preferably performed by performing a predetermined heat treatment after the silicone oil is adhered to the surface of the silica particles. The heat treatment is not particularly limited, but can be preferably performed in an environment of 100 ° C. to 300 ° C.

The reaction time may be appropriately determined according to the reactivity of the silicone oil to be used, but it is usually possible to obtain a sufficient reaction rate within 24 hours.

After the reaction, an inert gas such as nitrogen is introduced and circulated to complete the reaction, and the residual solvent is removed.

(Electrophotographic toner)
The electrophotographic toner of the present embodiment is characterized by including the silicone oil-treated silica particles of the present embodiment as an external additive in the toner composed of a binder resin, and has excellent fluidity and the formation of toner aggregates. Therefore, the occurrence of printing defects such as color loss and density unevenness can be suppressed.

As the binder resin for the toner, known resins such as styrene-acrylic copolymer resin, polyester resin, and epoxy resin can be used without particular limitation. The toner production method can be applied not only to a pulverization / kneading method but also to a toner obtained by a polymerization method such as suspension polymerization or emulsion polymerization.

In the electrophotographic toner of the present embodiment, the amount of the external additive composed of the silicone oil-treated silica particles of the present embodiment is not particularly limited, and may be an amount that makes the obtained toner have desired characteristics. Is preferably 0.05 to 5% by mass, and more preferably 0.1 to 4% by mass. Further, as the external additive added to the toner of the present embodiment, the silicone oil-treated silica particles of the present embodiment may be used alone, and may be mixed with other external additives depending on the intended performance. May be used. In the latter case, it is preferable that the total amount as the external additive is within the above range. The method for adding the external additive to the toner is not particularly limited, and a known method can be used.

The electrophotographic toner of this embodiment can be arbitrarily blended with other known constituent materials. Specifically, black colorants, color colorants such as cyan, magenta, and yellow, charge control agents, and mold release agents such as wax can be used without any limitation.

The electrophotographic toner of the present embodiment can be a black toner or a color toner by blending a colorant. Further, it can be suitably used in any one of electrophotographic systems such as magnetic one component, nonmagnetic one component, and two component.

Hereinafter, examples and comparative examples will be shown to specifically describe the embodiments, but the present invention is not limited to these examples. The physical properties and evaluation of silica particles and silicone oil-treated silica particles were measured by the following methods.

(Measurement of specific surface area)
The specific surface area of the silica particles and the silicone oil-treated silica particles was measured by a BET one-point method based on the amount of nitrogen adsorption using a Shibata Scientific Instruments industrial specific surface area measuring device SA-1000.

(Measurement of particle density)
A dry automatic densimeter AccuPyc1330 type 10 ml sample insert manufactured by Shimadzu Corporation was used, and He gas having a pressure of 0.16 Pa was used. The measuring temperature of the measuring device was kept at 25 ° C. by circulating hot water. In order to increase the sample filling amount as a sample pretreatment, uniaxial pressing was performed under the following conditions. Silica particles were packed into a cemented carbide press die having a diameter of 50 mm and a height of 75 mm, and compression molding was performed with a MH-15TON press (ram diameter 55 mm) manufactured by MASADASEISAKUSHO under a pressure of 15 tons. The pressure was released in about 2 seconds, and the sample was taken out from the mold. The compressed sample was dried for 8 hours under a pressure of 200 ° C.-0.095 PaG or less in a vacuum dryer, and then allowed to cool to room temperature under reduced pressure in the dryer.

(Measurement of α value by small angle X-ray scattering)
Silica particles were filled into a through-hole of a sample holder having a length of 40 mm, a width of 5 mm, and a thickness of 1 mm, and both sides of the filled sample were held by squeezing with a 6 μm-thick polypropylene film for measurement. Using a biaxial small-angle X-ray scattering device (M18XHF22) manufactured by Mac Science equipped with Kratzky U-slit, incident X-ray Cu-Kα ray, tube voltage 40 kV, tube current 300 mA, slit width 10 μm, detector scanning angle Measurements were taken from 0.025 degrees to 0.900 degrees. The measurement was performed 5 times per sample, and the average value was taken as the measured value. The obtained small-angle X-ray scattering curve is analyzed, and α values are calculated for the periodic structures having the sizes included in the measurement ranges of 20 to 30 nm, 30 to 50 nm, and 50 to 70 nm, respectively, and the maximum value is expressed as αmax value. did. Details of the α value measurement were performed by the method described in Japanese Patent No. 47756040. The contents of the patent are incorporated as part of the description of the present application.

(Apparent density measurement)
Measurement was carried out according to JIS 5101-12-1 pigment test method.

(Calculation method of silica surface silicone oil and free silicone oil)
In a centrifuge tube with a capacity of 50 ml, 0.5 g of a sample and 32 ml of normal hexane are put, and ultrasonically dispersed for 30 minutes in an ultrasonic cleaner 1510JMTH manufactured by Yamato Scientific, and suspended. The resulting suspension was centrifuged to separate and recover the solid phase (silica). To the recovered silica, 32 ml of normal hexane is further added, and the operations of ultrasonic dispersion and centrifugation are repeated three times in total, and dried under reduced pressure (120 ° C., 12 hours) to obtain a dry powder. The carbon content of this powder is measured using Sumika NC-22F manufactured by Sumika Chemical Analysis Co., Ltd. The total carbon content in 0.5 g of the sample was measured in advance, and the amount of extracted free silicone oil was calculated from the difference from the total carbon content. Further, the total amount of silicone oil present on the surface of the silicone oil-treated silica particles was calculated from the total carbon content in 0.5 g of the sample measured in advance.

Specifically, the carbon content corresponding to the above difference was converted to a silicone oil having a main chain of dimethylsiloxane (structural formula:-(Si (CH3) 2-O) n-) to obtain the amount of free silicone oil.

(Evaluation of cohesion)
(1. Preparation of pseudo toner)
Styrene-acrylic resin (manufactured by Sanyo Chemical Industries, Ltd., Hymer SB-317) was pulverized with a jet mill and measured with a laser scattering / diffraction particle size distribution analyzer (manufactured by Seishin Enterprise Co., Ltd., LMS-30). Resin powder having a unit diameter of 7 μm was used. Hymer SB-317 has a glass transition temperature of 60 ° C., a number average molecular weight of 4,000, a weight average molecular weight of 250,000, and a melt flow rate of 3.5 g / 10 min.

A volume of 250 ml of 35 g of the obtained resin powder, 0.7 g of the obtained silicone oil-treated silica particles (external additive), and 200 g of 5 mm glass beads (manufactured by ASONE Co., Ltd., glass beads BZ-5) Placed in an eyeboy wide mouth bottle (trade name, manufactured by As One Co., Ltd.) and installed in a horizontal state on a shaker (manufactured by Iwaki Sangyo Co., Ltd., KM Shaker V-SX). The mixture was shaken for 10 minutes at a speed of 280 times / minute.

After shaking, the glass beads were removed by sieving using a powder tester (manufactured by Hosokawa Micron Corporation, PT-X type). At this time, the opening of the sieve was 1.7 mm, the amplitude was 1 mm, and the vibration time was 180 seconds. The obtained powder was further allowed to stand for 24 hours or more under conditions of 25 ° C. and 50% relative humidity, and this was recovered as a pseudo toner.

(2. Measurement of cohesion)
The aggregation degree of the collected pseudo toner was measured using a powder tester (manufactured by Hosokawa Micron Corporation, PT-X type) using 2 g of the pseudo toner. The sieve openings were 150 μm, 75 μm, and 45 μm from the top. The amplitude was 1 mm and the vibration time was 30 seconds. The degree of aggregation is expressed by the following formula. It can be evaluated that the smaller the value of the degree of aggregation is, the less the amount of toner or silica is aggregated.

Aggregation degree (%) = (A + 0.6 × B + 0.2 × C) / 2 × 100
The values of A, B, and C in the formula are as follows.

A: Residual amount of pseudo toner sieve over 150 μm (g)
B: Residual amount of pseudo toner sieve on 75 μm (g)
C: pseudo toner sieve remaining amount (g) over 45 μm

(Evaluation method for color loss and density unevenness)
The toner for electrophotography prepared using the silicone oil-treated silica particles according to each of the examples and comparative examples as an external additive is filled in a toner cartridge of a commercially available copying machine, and is continuously printed on a copy sheet of 5 cm square. A solid image of was output. Thereafter, a solid image of 5 cm square was further output continuously for 500 sheets, and the number of sheets where color loss or density unevenness occurred in the 500 solid image portions was visually evaluated. With respect to color loss, a color loss score of 3 or more was measured as the occurrence of color loss and was evaluated according to the following criteria.
5: 0 images with color loss or density unevenness 4: 1-5 images with color loss or density unevenness 3: 6-20 images with color loss or density unevenness 2: Color loss Or 21 to 40 images with density unevenness 1: 41 or more images with color loss or density unevenness

(Examples and Comparative Examples)
Examples 1 to 4
<Base material manufacturing process>
A closed triple tube burner with an inner diameter of 100 mm in the center tube is installed in the closed reactor, and silicon tetrachloride (SiCl ₄ ) gas (hereinafter referred to as STC) and hydrogen are used as source gases in the center tube, and air and oxygen as auxiliary gases. And a mixed gas premixed with each other. Hydrogen and air were supplied to the first annular tube to form a pilot flame. Air was passed through the second annular tube to prevent silica particles from adhering to the burner. In the raw material gas, 1.15 times as much hydrogen as the theoretical hydrogen amount was supplied to the raw material gas having an STC of 100 mol%. The adiabatic flame temperature was changed to the temperatures shown in Table 1 by changing the amount of raw material gas and the amount of auxiliary gas to be put into the center pipe, and STC was subjected to flame hydrolysis. The adiabatic flame temperature can be calculated by the method described in “Study on generation of fumed silica” (Surface Science Vol. 5, No. 1, P. 35-39 published in 1984). In addition, the content of the said literature is integrated as a part of description in this-application specification. The pressure in the reactor during the combustion reaction was 10 kPaG or more. The apparent density of each of the obtained fumed silicas was 16 to 19 g / l. Each of the fumed silicas was compressed by a degassing press and adjusted to an apparent density of 22 to 23 g / L to obtain silica particles as a base material.

<Surface treatment process>
400 g of the obtained silica particles of the base material were put into a mixer vessel having a volume of 35 L, and while stirring, nitrogen was supplied to make the inside of the vessel a nitrogen atmosphere and heated to 270 ° C. The container was not sealed, and the dimethyl silicone oil having a viscosity of 50 cSt was sprayed with the addition amount shown in Table 1 on the silica particles of the base material using a two-fluid nozzle while the container was open. After spraying, the mixture was stirred for 1 hour while maintaining the above atmosphere and temperature to obtain silicone oil-treated silica particles. The production conditions and physical property evaluation results are shown in Table 1.

Example 5
In the base material manufacturing process, the raw material gas supplied to the central tube of the triple tube burner was changed to STC to obtain methyltrichlorosilane. Further, in the raw material gas, 1.50 times as much hydrogen as the theoretical hydrogen amount was supplied to the raw material gas containing 100% by mole of methyltrichlorosilane. Furthermore, the adiabatic flame temperature was set to 2040 ° C. by changing the amount of raw material gas and the amount of auxiliary combustion gas to be placed in the center tube, and methyltrichlorosilane was subjected to flame hydrolysis. By changing the compression conditions in the degassing press of the obtained fumed silica, the apparent density of the silica particles of the base material was set to 27 g / L. Other manufacturing conditions were the same as in Example 1. The production conditions and physical property evaluation results are shown in Table 1.

Example 6
In the surface treatment step, the amount of dimethyl silicone oil sprayed by the two-fluid nozzle was 14 wt% with respect to the silica particles of the base material. Other manufacturing conditions were the same as in Example 1. The production conditions and physical property evaluation results are shown in Table 1.

Example 7
In the base material manufacturing process, the apparent density of the silica particles of the base material was set to 39 g / L by changing the compression conditions in the degassing press of fumed silica. Other manufacturing conditions were the same as in Example 1. The production conditions and physical property evaluation results are shown in Table 1.

Example 8
In the base material manufacturing process, the composition of the raw material gas put into the center tube was STC 90 mol% and methyldichlorosilane 10 mol%. Further, 1.30 times as much hydrogen as the theoretical hydrogen amount was supplied to the raw material gas. Furthermore, the adiabatic flame temperature was set to 2140 ° C. by hydrolyzing by changing the amount of raw material gas and the amount of auxiliary combustion gas put into the center pipe. Other manufacturing conditions were the same as in Example 1. The production conditions and physical property evaluation results are shown in Table 1.

Comparative Example 1
In the base material manufacturing process, the adiabatic flame temperature was set to 2050 ° C. by changing the amount of raw material gas and the amount of auxiliary gas to be put into the central tube. The apparent density of the silica particles of the base material was set to 25 g / L by changing the compression conditions in the degassing press of the obtained fumed silica. In the surface treatment step, the amount of dimethyl silicone oil sprayed was 9 wt% with respect to the silica particles of the base material. Other manufacturing conditions were the same as in Example 1. The production conditions and physical property evaluation results are shown in Table 2.

Comparative Example 2
In the base material manufacturing process, the adiabatic flame temperature was set to 1870 ° C. by changing the amount of raw material gas and the amount of auxiliary combustion gas to be put into the central tube. By changing the compression conditions in the degassing press of the obtained fumed silica, the apparent density of the silica particles of the substrate was set to 23 g / L. In the surface treatment step, the amount of dimethyl silicone oil sprayed was 20 wt% with respect to the silica particles of the base material. Other manufacturing conditions were the same as in Example 1. The production conditions and physical property evaluation results are shown in Table 2.

Comparative Example 3
In the base material manufacturing process, the apparent density of the silica particles of the base material was set to 19 g / L by changing the compression conditions in the degassing press of fumed silica. Other manufacturing conditions were the same as in Example 1. The production conditions and physical property evaluation results are shown in Table 2.

Comparative Example 4
In the surface treatment step, the amount of dimethyl silicone oil sprayed by the two-fluid nozzle was 9 wt% with respect to the silica particles of the base material. Other manufacturing conditions were the same as in Example 1. The production conditions and physical property evaluation results are shown in Table 2.

Comparative Example 5
In the base material manufacturing process, the apparent density of the silica particles of the base material was set to 24 g / L by changing the compression conditions in the degassing press of fumed silica. In the surface treatment step, the amount of dimethyl silicone oil sprayed by the two-fluid nozzle was 20 wt% with respect to the silica particles of the base material. Other manufacturing conditions were the same as in Example 1. The production conditions and physical property evaluation results are shown in Table 2.

Silica particles of Example 1-8, In the toner using the same, and silicone oil-treated silica particles, BET specific surface area of the silica particles is ^70m 2 / g or more 120 m ² / g or less (more specifically, ^{75 m} 2 / g to 100 m ² / g), the amount of the free silicone oil is 2.0% by mass or more and 5.0% by mass or less with respect to the silica particle body, and the degree of aggregation of the pseudo toner is 18% or less. Thus, it can be seen that these three conditions are all satisfied, and there is little color loss and density unevenness at the time of printing, and it is a toner external additive with excellent print quality.

Meanwhile silica particles of Comparative Example 1, the toner using the same and a silicone oil-treated silica particles, is ^{65 m} 2 / g is a BET specific surface area is less than ^70m 2 / g, degree of aggregation is large and 30% at the time of printing There are many color loss and density unevenness.

Silica particles of Comparative Example 2, the toners using silicone oil-treated silica particles and it, since a BET specific surface area is larger 140 m 2 / ^g than 120 m 2 / ^g, often color loss and density unevenness in printing.

In the silica particles of Comparative Example 3, the silicone oil-treated silica particles, and the toner using the same, the aggregation degree of the pseudo toner is 25%, which is larger than 18%, so that there are many color loss and density unevenness during printing.

In the silica particles of Comparative Example 4, the silicone oil-treated silica particles and the toner using the same, the amount of free silicone oil is 1% by mass, which is less than 2.0% by mass with respect to the silica particle main body. There are many color loss and density unevenness.

In the silica particles of Comparative Example 5, the silica particles treated with silicone oil, and the toner using the same, the amount of free silicone oil is 10% by mass, which is much more than 5.0% by mass with respect to the silica particle body. There are many color loss and density unevenness.

(Other embodiments)
The above-described embodiments and examples are examples of the present invention, and the present invention is not limited to these examples, and these examples may be combined with or partially replaced with known techniques, common techniques, and known techniques. Good. Also, modified inventions easily conceived by those skilled in the art are included in the present invention.

Claims

Silicone oil-treated silica particles comprising a silica particle body and silicone oil,
The BET specific surface area of the silica particle body is 70 m 2 / g or more and 120 m 2 / g or less,
The silica particle body is surface-treated with the silicone oil,
Of the silicone oil, the amount of free silicone oil released from the surface of the silica particle body is 2.0% by mass or more and 5.0% by mass or less based on the silica particle body.
The aggregation degree of the surface-treated styrene acrylic resin particles in which 2 parts by mass of the silicone oil-treated silica particles are mixed with 100 parts by mass of the styrene acrylic resin particles having a median particle diameter of 5 μm or more and 8 μm or less is 18% or less. Silicone oil treated silica particles.
2. The silicone according to claim 1, wherein a maximum value αmax of fractal shape parameter α values in the measurement ranges of 20 to 30 nm, 30 to 40 nm, and 50 to 70 nm of the silica particle body is 2.9 or more. Oil-treated silica particles.
The silicone oil-treated silica particles according to claim 1 or 2, wherein the silica particle body has a particle density measured by a He gas pycnometer method of 2.23 g / cm 3 or more.
The silicone oil-treated silica particles according to any one of claims 1 to 3, wherein an apparent density of the silica particle main body is 20 g / l or more and 35 g / l or less.
An electrophotographic toner containing the silicone oil-treated silica particles according to any one of claims 1 to 4 as an external additive.
Preparing a silica particle main body having a BET specific surface area of 70 m 2 / g or more and 120 m 2 / g or less;
A method for producing silicone oil-treated silica particles, comprising: adding silicone oil to the silica particle body and coating the surface of the silica particle body with silicone oil.