Fine powder for toner and toner

Abstract

To provide fine powder for toner that can improve cleaning properties while preventing a reduction in developability due to contamination.SOLUTION: The present disclosure relates to fine powder for toner having silicone oil. With reference to the number of all silicon atoms, the dispensed silicone oil is such that: the number ratio of the silicon atoms having a Q unit structure is 1% or more and 40% or less, the total sum of the number ratio of the silicon atoms having a D unit structure and the number ratio of the silicon atoms having an M unit structure is 60% or more and 99% or less, and the content of the dispensed silicone oil is 0.1 mass% or more and 10.0 mass% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a fine powder for toner and a toner using the fine powder for toner. [Background technology]

[0002] In recent years, as electrophotographic full-color copying machines have become more widespread, there has been a demand for even higher image quality, and toner particle size has been reduced. However, as the toner particle size decreases, the toner becomes more difficult to scrape off by a cleaning blade during the cleaning process, and tends to slip through the cleaning blade, which is known as a cleaning failure. As a means for improving cleaning performance, a method is known in which inorganic fine particles treated with silicone oil are used as an external additive to strengthen the blocking layer (external additive blocking layer) formed by the external additive near the cleaning blade nip (Patent Documents 1 and 2). Another method is known in which resin fine particles containing silicone oil are incorporated into the toner (Patent Document 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-78779 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-57459 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-58468 Summary of the Invention [Problem to be solved by the invention]

[0004] When fine particles treated with linear silicone oil are used as an external additive as in Patent Documents 1 and 2, the silicone oil contaminates the carrier and components, resulting in a problem of reduced developability. In addition, in Patent Document 3, silicone oil is encapsulated in resin microparticles, but because the resin microparticles are soft, stress within the developing machine can cause the resin microparticles to collapse, exposing the silicone oil, which also poses the problem of reduced developability. An object of the present invention is to provide a fine powder for a toner and a toner that solves the above-mentioned problems, specifically, to provide a fine powder for a toner and a toner that can improve cleaning properties while suppressing deterioration of developability due to contamination. [Means for solving the problem]

[0005] The present invention provides a fine powder for toner containing silicone oil, The silicone oil fractionated by the following fractionation method has the following composition, based on the number of all silicon atoms: (i) the ratio X1 (%) of the number of silicon atoms having the structure represented by formula (1) is 1% or more and 40% or less, (ii) the sum of the number ratio X2 (%) of silicon atoms having the structure represented by formula (2) and the number ratio X3 (%) of silicon atoms having the structure represented by formula (3) is 60% or more and 99% or less; the content of the separated silicone oil is 0.1% by mass or more and 10.0% by mass or less based on the mass of the fine powder for toner; The present invention relates to a fine powder for toner, characterized in that: ·Preparative method: a) 10 g of fine powder for toner is dispersed in 200 mL of hexane and subjected to ultrasonic treatment (frequency 30 kHz, output capacity 15 W, intensity 100%, time 5 minutes). b) After the ultrasonic treatment, the dispersion is subjected to suction filtration. c) The hexane is distilled off from the filtrate to obtain silicone oil.

[0006] [ka] (R1, R2, and R4 to R6 each independently represent an alkyl group having 1 to 6 carbon atoms.) The present disclosure also provides a toner having toner particles and fine powder adhering to or adhering to the surfaces of the toner particles, wherein the fine powder is the above-described fine powder for toner. [Effects of the Invention]

[0007] When the fine powder for toner of the present disclosure is used, the cleaning property can be improved without impairing the developability. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram of a heat treatment apparatus used in the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0009] In the present disclosure, unless otherwise specified, the expressions "xx or more and xx or less" and "xx to xx" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints.

[0010] [The process and significance of this disclosure] The present inventors believe that the mechanism by which the effects of the present disclosure are realized is as follows.

[0011] Conventionally, silicone oils used to improve the fluidity and cleaning properties of external additives have generally been relatively low-viscosity straight-chain oils consisting of D and M units, such as dimethyl silicone oil. When external additives are treated with such straight-chain silicone oils, the effect of the free oil strengthens the external additive blocking layer (hereinafter also referred to as "blocking layer") in the cleaning area compared to the untreated case, but this contaminates the carrier and components, resulting in reduced developability.

[0012] On the other hand, the silicone oil of the present disclosure has a cross-linked structure that includes Q unit in addition to D unit and M unit.When fine powder is treated with the silicone oil of this cross-linked structure, when the fine powder contacts each other in the blocking layer and pressure is applied, the blocking layer is strengthened by the entanglement of the molecular chain of oil.In addition, because it is harder oil than the straight-chain silicone oil, it can be thought that it can suppress the contamination of carrier and component, and thus the present disclosure has been reached.

[0013] [Fine powder for toner] The composition of the fine powder according to the present disclosure will be described in detail below.

[0014] The toner fine powder of the present disclosure is a toner fine powder containing silicone oil, The silicone oil fractionated by the following fractionation method has the following composition, based on the number of all silicon atoms: (i) the ratio X1 (%) of the number of silicon atoms having the structure represented by formula (1) is 1% or more and 40% or less, (ii) the sum of the number ratio X2 (%) of silicon atoms having the structure represented by formula (2) and the number ratio X3 (%) of silicon atoms having the structure represented by formula (3) is 60% or more and 99% or less; the content of the separated silicone oil is 0.1% by mass or more and 10.0% by mass or less based on the mass of the fine powder for toner; It is characterized by: ·Preparative method: a) 10 g of fine powder for toner is dispersed in 200 mL of hexane and subjected to ultrasonic treatment (frequency 30 kHz, output capacity 15 W, intensity 100%, time 5 minutes). b) After the ultrasonic treatment, the dispersion is subjected to suction filtration. c) The hexane is distilled off from the filtrate to obtain silicone oil.

[0015] [ka] (R1, R2, and R4 to R6 each independently represent an alkyl group having 1 to 6 carbon atoms.)

[0016] In the silicone oil for toner fine powder according to the present disclosure, the proportion X1 of silicon atoms having the structure represented by formula (1) is 1% or more and 40% or less, based on the total number of silicon atoms. When the proportion X1 is within the above range, the oil is appropriately crosslinked and hardened, thereby suppressing contamination of carriers and components.

[0017] The number ratio X1 is preferably in the range of 5% to 30%, more preferably 10% to 30%.

[0018] In addition, the silicone oil separated by the above method has a total of 60% to 99% of the number proportion X2 of silicon atoms having the structure represented by formula (2) and the number proportion X3 of silicon atoms having the structure represented by formula (3) based on the total number of silicon atoms. If the total number proportion of silicon atoms of formula (2) and formula (3) is within the above range, it is an oily compound, so it can be used to process fine powder.

[0019] The total proportion of the number of silicon atoms (X2+X3) is preferably in the range of 70% to 95%, more preferably 75% to 90%.

[0020] The method for producing silicone oil is not particularly limited. For example, silicone oil can be obtained by adding a silane compound dropwise to water and subjecting it to a hydrolysis and condensation reaction in the presence of a catalyst. The degree of crosslinking can be controlled by the type of catalyst, pH, the blending ratio of the silane compound, reaction temperature, reaction time, etc. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include, but are not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide. Details will be described later.

[0021] The silicone oil content of the toner fine powder of the present disclosure is 0.1% by mass or more and 10.0% by mass or less, based on the mass of the toner fine powder. When the silicone oil content is within this range, the silicone oil strengthens the blocking layer and improves cleaning properties. The silicone oil content is preferably in the range of 0.5% by mass or more and 5.0% by mass or less, and more preferably 1.0% by mass or more and 5.0% by mass or less.

[0022] The separated silicone oil preferably satisfies the following formula: 1.0≦X2 / X1≦20.0

[0023] When X2 / X1 is within the above range, the silicone oil has an appropriate degree of crosslinking, which improves cleaning properties and prevents contamination. From the above viewpoint, X2 / X1 is more preferably 1.5 or more and 7.0 or less.

[0024] The number average molecular weight of the separated silicone oil is preferably 300 or more and 3000 or less. When the molecular weight is within the above range, the molecular chains of the silicone oil are easily entangled, the blocking layer is strengthened, and cleaning properties can be improved. From the above viewpoint, the molecular weight is more preferably 500 or more and 1500 or less.

[0025] The kinetic viscosity of the silicone oil was 100 mm 2 / s or more 10000mm 2 When the kinematic viscosity is within the above range, the effect of strengthening the blocking layer can be obtained while suppressing contamination of components. 2 / s or more 5000mm 2 From the above viewpoint, it is more preferable that the saturation rate is 1 / s or less.

[0026] The kinetic viscosity of silicone oil can be controlled by the compounding ratio of silane compounds, reaction temperature, reaction time, and pH. For example, methods for increasing the kinetic viscosity include increasing the proportion of tetrafunctional or trifunctional silane monomers, increasing the reaction temperature, and extending the reaction time. Methods for decreasing the kinetic viscosity include increasing the proportion of bifunctional silane monomers, decreasing the reaction temperature, and shortening the reaction time.

[0027] On the other hand, the particles obtained by drying the residue filtered out by the above-mentioned fractionation method (fine powder after removing the silicone oil) are preferably organosilicon polymer particles having the structure of the above-mentioned formula (1), the structure of formula (2), the structure of formula (3), or the structure of the following formula (4).Since organosilicon polymer particles have a structure similar to that of silicone oil, they have improved adhesion to silicone oil and can effectively suppress contamination.

[0028] [ka] (R3 represents an alkyl group having 1 to 6 carbon atoms.)

[0029] Furthermore, with respect to particles obtained by drying the filtered residue, when the ratio of the number of silicon atoms having the structure represented by formula (1) is Y1 (%) and the ratio of the number of silicon atoms having the structure represented by formula (2) is Y2 (%) based on the total number of silicon atoms contained in the particles obtained by drying the filtered residue, it is preferable that X1, X2, Y1, and Y2 satisfy the following formula: 0≦(Y2 / Y1) / (X2 / X1)≦3.0

[0030] When (Y2 / Y1) / (X2 / X1) is within the above range, the silicone oil and the fine powder have similar structures, which improves adhesion to the oil and suppresses contamination. It is more preferable that (Y2 / Y1) / (X2 / X1) is 0.3 or more and 0.7 or less.

[0031] There are no particular limitations on the method for producing organosilicon polymer particles. For example, a silane compound can be added dropwise to water, hydrolyzed and condensed in the presence of a catalyst, and the resulting suspension can be filtered and dried. The particle size can be controlled by the type of catalyst, the compounding ratio, the reaction initiation temperature, the dropwise addition time, and other factors. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include, but are not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide. Details will be provided below.

[0032] The particles obtained by filtering the residue obtained by the above-mentioned fractionation method and drying the residue preferably have pores. Furthermore, the volume average diameter of the pores is 5 nm or more and 20 nm or less, and the average volume of the pores is 0.3 cm. 3 / g or more 1.0cm 3 / g or less is more preferable. When the fine powder has pores within the above range, silicone oil can be retained not only on the surface but also inside. When oil is present inside, the oil seeps out when pressure is applied in the cleaning process, strengthening the blocking layer, but when pressure is not applied, the oil is retained inside, thereby suppressing contamination. The volume average diameter of the pores is 10 nm or more and 20 nm or less, and the average volume is 0.3 cm 3 / g or more 0.6cm 3 From the above viewpoint, it is more preferable that the saturation coefficient is 1 / g or less.

[0033] In wet production methods, the average pore size and volume can be controlled by adjusting the hydrolysis and condensation conditions (reaction temperature, reaction time, and stirring time), pH, catalyst type, and the ratio of added monomers. For example, increasing the pore size can be achieved by increasing the ratio of bifunctional silane, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the solution pH, and lowering the temperature during hydrolysis. Reducing the pore size can be achieved by increasing the ratio of tetrafunctional silane, increasing the temperature during the condensation reaction, lengthening the stirring time, increasing the solution pH, and increasing the temperature during hydrolysis. Reducing the pore volume can be achieved by increasing the ratio of bifunctional silane, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the solution pH, and lowering the temperature during hydrolysis. To reduce this, methods include increasing the mixing ratio of tetrafunctional silane, increasing the temperature during the condensation reaction, extending the stirring time, increasing the pH of the solution, or increasing the temperature during hydrolysis.

[0034] The number-average particle diameter of the toner fine powder is preferably 80 nm or more and 150 nm or less. Within this range, the fine powder is less likely to slip through the cleaning blade, and a blocking layer can be formed. From the above viewpoint, the number-average particle diameter is more preferably 90 nm or more and 130 nm or less.

[0035] In the toner fine powder of the present disclosure, the particles obtained by drying the filtered residue obtained by the above-mentioned fractionation method are preferably composite fine particles. The composite fine particles preferably comprise base particles made of an organosilicon polymer having a structure represented by formula (1), (2), (3), or (4), and convex particles present on the surface of the base particles, at least partially embedded in the surface. When the fine powder has a shape with convex portions as described above, the convex portions interlock with each other in the blocking layer, forming a stronger blocking layer. Any particle can be selected as the particle that forms the convex portions, but silica fine particles are preferred. A method for combining the convex particles with the base particles made of an organosilicon polymer will be described later.

[0036] The toner fine powder preferably has a compression cohesion value of 100 mJ or more at 60 kPa. Within this range, the cohesion force is sufficient when pressure is applied in the cleaning section, making it possible to form a strong blocking layer. From the above perspective, it is more preferable that the compression cohesion value be 110 mJ or more.

[0037] <Silicone oil manufacturing method> The production method is not particularly limited, but synthesis via hydrolysis and condensation polymerization of a silicon compound (silane monomer) in an aqueous system is preferred. Specifically, a mixture of a bifunctional silane having two siloxane bonds and a tetrafunctional silane having four siloxane bonds is preferably hydrolyzed and condensed using a catalyst. Silane monomers such as bifunctional silanes and tetrafunctional silanes will be described later. The degree of crosslinking and molecular weight can be controlled by the type of catalyst, the compounding ratio, reaction temperature, reaction time, etc. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include, but are not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide. The amount of catalyst used can be adjusted appropriately depending on the type of silicon compound and catalyst. The reaction temperature is not particularly limited, and a range of 5 to 70°C is preferably selected taking productivity and other factors into consideration.

[0038] The monomer to be used can be appropriately selected based on its compatibility with the solvent and catalyst, its hydrolysis property, etc. Examples of the tetrafunctional silane monomer having the structure (1) above include tetramethoxysilane, tetraethoxysilane, and tetraisocyanatesilane, with tetraethoxysilane being preferred.

[0039] Examples of bifunctional silane monomers having the structure (2) above include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and dimethoxydiethylsilane, and among these, dimethoxydimethylsilane is preferred.

[0040] Examples of monofunctional silane monomers that form the structure represented by formula (3) include t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, and triphenylethoxysilane.

[0041] Examples of trifunctional silane monomers having the structure (4) include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethoxyhydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, Examples of such silane include ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane. Of these, methyltrimethoxysilane is preferred.

[0042] <Method for producing organosilicon polymer composite particles> Although the manufacturing method is not particularly limited, it is preferable to form particles through hydrolysis and condensation polymerization of a silicon compound (silane monomer) by the sol-gel method. Specifically, it is preferable to hydrolyze and condense a mixture of a bifunctional silane having two siloxane bonds and a tetrafunctional silane having four siloxane bonds, and then react with colloidal silica or the like to form composite particles of an organosilicon polymer. Silane monomers such as bifunctional silanes and tetrafunctional silanes will be described later. The proportion of bifunctional silane is preferably 30 mol% to 70 mol%, more preferably 40 mol% to 60 mol%. The proportion of tetrafunctional silane is preferably 30 mol% to 80 mol%, more preferably 40 mol% to 70 mol%.

[0043] There are no particular limitations on the method for producing organosilicon polymers. For example, a silane compound can be added dropwise to water, hydrolyzed and condensed in the presence of a catalyst, and the resulting suspension can be filtered and dried. The particle size can be controlled by the type of catalyst, the compounding ratio, the reaction initiation temperature, the dropwise addition time, etc. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include, but are not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0044] The organosilicon polymer is preferably produced by the following method. Specifically, a first step of obtaining a hydrolyzate of a silicon compound; a second step of mixing the hydrolyzate with an alkaline aqueous medium and colloidal silica to cause a polycondensation reaction of the hydrolyzate with the colloidal silica; and The third step is mixing the polycondensation reactant with the aqueous solution and forming particles. In some cases, a hydrophobizing agent such as hexamethyldisilazane may be further blended.

[0045] In the first step, a silicon compound is contacted with a catalyst by stirring, mixing, or the like in an aqueous solution in which an acidic or alkaline substance serving as a catalyst is dissolved in water. Known catalysts can be suitably used. Specific examples of acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0046] The amount of catalyst used may be adjusted appropriately depending on the type of silicon compound and catalyst. Preferably, the amount of catalyst used is 1×10 -3 The amount of catalyst used is selected from the range of 1×10 to 1 part by mass. -3 If the amount of catalyst used is 1 part by mass or more, the reaction will proceed sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles will be low, making hydrolysis easier. The amount of water used is preferably 2 to 15 moles per mole of silicon compound. If the amount of water used is 2 moles or more, the hydrolysis reaction will proceed sufficiently, and if it is 15 moles or less, productivity will improve.

[0047] The reaction temperature is not particularly limited and may be carried out at room temperature or under heated conditions, but it is preferable to carry out the reaction at a temperature maintained at 10 to 60° C., as this allows a hydrolysate to be obtained in a short time and prevents a partial condensation reaction of the produced hydrolysate. The reaction time is not particularly limited and may be appropriately selected taking into consideration the reactivity of the silicon compound used, the composition of the reaction liquid obtained by mixing the silicon compound, acid, and water, and productivity.

[0048] In the second step of the method for producing silicon polymer microparticles, the raw material solution obtained in the first step is mixed with an alkaline aqueous medium to polycondense the particle precursors, thereby obtaining a polycondensation reaction solution. The alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0049] The alkaline component used in the alkaline aqueous medium is one whose aqueous solution is basic and acts as a neutralizer for the catalyst used in step 1 and as a catalyst for the polycondensation reaction in step 2. Examples of such alkaline components include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine.

[0050] The amount of the alkali component used is an amount that neutralizes the acid and effectively acts as a catalyst for the polycondensation reaction. For example, when ammonia is used as the alkali component, the amount is usually selected in the range of 0.01 parts by mass or more and 12.5 parts by mass or less per 100 parts by mass of the mixture of water and the organic solvent.

[0051] In the second step, in order to prepare an alkaline aqueous medium, an organic solvent may be used in addition to the alkaline component and water. The organic solvent is not particularly limited as long as it is compatible with water, but an organic solvent that dissolves 10 g or more of water per 100 g at room temperature and normal pressure is preferred.

[0052] Specific examples include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethers such as ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0053] Among the organic solvents listed above, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, etc. are preferred. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reactions, it is more preferred to select as the organic solvent the same alcohol as the alcohol produced by elimination.

[0054] In the second step, colloidal silica is mixed to form composite microparticles in which convex particles are present, at least partially embedded, on the surface of the organosilicon polymer base particle. The presence of multiple convex particles on the organosilicon polymer surface further strengthens the interlocking prevention layer between the composite microparticles, as the convex portions originating from the convex particles form. The convex portions originating from the convex particles present on the organosilicon polymer surface can be confirmed by observing the composite microparticles with a scanning electron microscope (SEM).

[0055] In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. Water (tap water, pure water, etc.) is preferably used as the aqueous solution, but components compatible with water, such as salts, acids, alkalis, organic solvents, surfactants, and water-soluble polymers, may also be added to the water. The temperatures of the polycondensation reaction liquid and the aqueous solution when mixed are not particularly limited, and are preferably selected in the range of 5 to 70°C, taking into consideration the composition, productivity, etc.

[0056] The method for recovering particles can be any known method without any particular limitation. For example, a method of scooping floating powder or a filtration method can be mentioned, but filtration is preferred because of its simple operation. The filtration method is not particularly limited, and known devices such as vacuum filtration, centrifugal filtration, and pressure filtration can be selected. The filter paper, filter, filter cloth, etc. used for filtration are not particularly limited as long as they are industrially available, and can be appropriately selected depending on the device used.

[0057] The monomer to be used can be appropriately selected depending on the compatibility with the solvent and catalyst, or on hydrolysis property, and the monomers exemplified as silicone oil monomers can be used in the same way.

[0058] <Method of treating base particles with silicone oil> The method of treating the base particles of the toner fine powder with silicone oil is not particularly limited. The base particles and silicone oil may be produced separately, and then treated with a wet or dry method. In particular, when treating with a wet method, the synthesis of silicone oil and the surface treatment can be performed simultaneously by adding a silane monomer and a catalyst, which are the raw materials for the silicone oil, to the dispersion of the base particles before filtration and stirring. Furthermore, other surface treatment agents such as hexamethyldisilazane may also be used in combination with silicone oil.

[0059] [Toner particles] Next, the composition of the toner particles will be described.

[0060] <Binder resin> The binder resin used in the toner is not particularly limited, and the following polymers or resins can be used.

[0061] Examples of suitable materials include homopolymers of styrene and its substituted derivatives, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers; and polyvinyl chloride, phenolic resins, naturally modified phenolic resins, naturally modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins. Among these, polyester resins are preferred from the viewpoints of durability and charging stability. In addition, from the viewpoint of environmental stability and charging stability, the acid value of the polyester resin is preferably 0.5 mgKOH / g or more and 40 mgKOH / g or less. The acid group in the polyester resin and the Si-CH3 in the fine powder interact with each other, which can further improve the toner charging property in a high-humidity environment. The acid value is more preferably 1 mgKOH / g or more and 20 mgKOH / g or less, and even more preferably 1 mgKOH / g or more and 15 mgKOH / g or less.

[0062] <Coloring agent> The toner may contain a colorant, if necessary. Examples of the colorant include the following.

[0063] Examples of black colorants include carbon black and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the clarity from the viewpoint of the image quality of a full-color image.

[0064] Examples of pigments for magenta toner include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0065] Dyes for magenta toner include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0066] Examples of pigments for cyan toner include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; and CI Acid Blue 45, and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

[0067] An example of a dye for cyan toner is CI Solvent Blue 70.

[0068] Yellow toner pigments include the following: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Vat Yellow 1, 3, 20.

[0069] An example of a yellow toner dye is CI Solvent Yellow 162.

[0070] The content of the colorant is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0071] <Wax> The toner may contain wax as needed. Examples of wax include the following.

[0072] Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or their block copolymers; waxes whose main component is fatty acid esters such as carnauba wax; partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0073] Further examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene Saturated fatty acid bisamides such as bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearyl isophthalamide; fatty metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.

[0074] The content of the wax is preferably 2.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0075] <Charge control agent> The toner may contain a charge control agent as needed. Known charge control agents can be used as the charge control agent contained in the toner, but particularly preferred are metal compounds of aromatic carboxylic acids, which are colorless, can charge the toner quickly, and can stably maintain a constant charge amount.

[0076] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate or sulfonate ester on the side chain, polymeric compounds having carboxylate or carboxylate ester on the side chain, boron compounds, urea compounds, silicon compounds, and calixarene. The charge control agent may be added internally or externally to the toner particles.

[0077] The amount of the charge control agent added is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0078] [toner] The toner according to the present disclosure comprises toner particles and fine powder for toner that adheres or adheres to the surfaces of the toner particles.

[0079] <Content of fine powder for toner> The content of the fine powder for toner of the present disclosure is preferably 0.1 to 20.0 parts by mass per 100 parts by mass of toner particles in terms of strengthening the blocking layer and suppressing contamination of the carrier and components. It is further preferably 0.5 to 15.0 parts by mass, and even more preferably 1.0 to 10.0 parts by mass.

[0080] If the content of the toner fine powder is less than 0.1 parts by mass, it becomes difficult to obtain the effect of strengthening the blocking layer. On the other hand, if the content of the toner fine powder is more than 20.0 parts by mass, filming of the fine powder particles onto the carrier, charging member, and photosensitive member may occur when images are output for a long period of time.

[0081] <Inorganic fine powder> In addition to the above-described fine powder for toner, other inorganic fine powders can also be used in combination with the toner as needed. The inorganic fine powders used in combination may be added internally to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powders such as silica are preferred. The inorganic fine powders used in combination are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0082] As an external additive to improve fluidity, 2 / g or more 400m 2 / g or less of inorganic fine powder is preferred. The inorganic fine powder is preferably used in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of toner particles. When the above range is satisfied, the effect of charge stability is easily obtained.

[0083] [Developer] The toner can be used as a one-component developer, but in order to further improve dot reproducibility and long-term stability, it is preferable to mix the toner with a magnetic carrier and use it as a two-component developer.

[0084] Examples of magnetic carriers that can be used include generally known magnetic carriers such as surface-oxidized iron powder, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, oxide particles, and magnetic materials such as ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state.

[0085] When the toner is mixed with a magnetic carrier to be used as a two-component developer, good results are usually obtained when the carrier mixing ratio is, in terms of toner concentration in the two-component developer, preferably 2% by mass or more and 15% by mass or less, and more preferably 4% by mass or more and 13% by mass or less.

[0086] [Method of manufacturing toner particles and method of manufacturing toner] The method for producing toner particles is not particularly limited, and any of the conventionally known production methods such as suspension polymerization, emulsion aggregation, melt-kneading, and dissolution suspension methods can be used.

[0087] The toner particles thus obtained can be mixed with the fine powder for toner of the present disclosure and, if necessary, the other external additives described above to obtain a toner. The toner particles can be mixed with the fine powder for toner of the present disclosure and the other external additives using a mixing device such as a double con mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0088] Furthermore, in order to control the adhesion rate of the fine powder for toner to the toner particles, it is preferable to mix the fine powder for toner with the toner particles to obtain a toner particle mixture and then perform a heat treatment. For example, the heat treatment can be performed with hot air using a heat treatment device shown in Figure 1.

[0089] The heat treatment device has a treatment chamber 6 for heat-treating the toner particle mixture, a toner particle mixture supply means for supplying the toner particle mixture to the treatment chamber 6, a hot air supply means 7 for supplying hot air for heat-treating the toner particle mixture supplied from the toner particle mixture supply means, and a recovery means 10 for discharging the heat-treated toner particles outside the treatment chamber 6 from an outlet provided in the treatment chamber 6 and recovering them.

[0090] 1 further includes a regulating means 9 as a cylindrical member, and the processing chamber 6 has a cylindrical shape that covers the outer peripheral surface of the regulating means 9. The hot air supplying means 7 is provided at one end of the cylindrical shape of the processing chamber 6 so that the hot air flows while rotating inside the cylindrical processing chamber 6. The toner particle mixture supplying means is composed of a plurality of supply pipes 5 provided on the outer periphery of the processing chamber 6.

[0091] Furthermore, the discharge port provided in the treatment chamber 6 is provided on the outer periphery of the end of the treatment chamber 6 on the side opposite to the side where the hot air supply means 7 is provided, so as to be on an extension of the rotation direction of the toner particle mixture. Heat treatment using a heat treatment device having the above-mentioned configuration will be described below.

[0092] The toner particle mixture supplied by the raw material constant-quantity supply means 1 is introduced into an introduction pipe 3, which is installed vertically to the raw material constant-quantity supply means 1, by compressed gas adjusted by a compressed gas flow rate adjustment means 2. The mixture that passes through the introduction pipe is uniformly dispersed by a conical protruding member 4 provided in the center of the raw material constant-quantity supply means 1, and is then introduced into eight supply pipes 5 that radiate outward, and into a treatment chamber 6 where heat treatment is carried out.

[0093] At this time, the flow of the mixture supplied to the processing chamber 6 is regulated by a regulating means 9 for regulating the flow of the mixture, which is provided in the processing chamber 6. Therefore, the mixture supplied to the processing chamber is heat-treated while swirling inside the processing chamber 6, and then cooled.

[0094] Heat for heat-treating the supplied mixture is supplied from hot air supply means 7, distributed by distribution member 12, and introduced into treatment chamber 6 by swirling member 13 for swirling the hot air in a spiral shape. The swirling member 13 for swirling the hot air has multiple blades, and the swirling of the hot air can be controlled by the number and angle of the blades. Hot air is supplied from hot air supply means outlet 11.

[0095] The heat-treated toner particles are cooled by cold air supplied from the cold air supplying means 8 (cold air supplying means 8-1, 8-2 and 8-3).

[0096] Next, the cooled toner particles are collected as toner by the collecting means 10 at the bottom end of the processing chamber. A blower (not shown) is provided ahead of the collecting means, and the toner particles are sucked and transported by the blower.

[0097] The powder particle supply port 14 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are the same, and the recovery means 10 of the thermal sphering treatment device is provided on the outer periphery of the treatment chamber so as to maintain the swirling direction of the swirled powder particles. Furthermore, the cold air supplied from the cold air supply means 8 is configured to be supplied from the outer periphery of the device to the circumferential surface inside the treatment chamber in a horizontal and tangential direction.

[0098] The fine powder for toner of the present disclosure preferably has an adhesion rate to toner particles of 30% to 80%. When the adhesion rate is within this range, an amount of fine powder suitable for forming a blocking layer is supplied to the cleaning section.

[0099] [Image forming equipment] When using a toner, an image forming apparatus is used which includes a support, an electrophotographic photosensitive member having a photosensitive layer formed on the support, an image forming means for forming an electrostatic image on the electrophotographic photosensitive member, a developing means for supplying toner to the electrostatic image formed on the electrophotographic photosensitive member, a transfer means for transferring the toner image from the electrophotographic photosensitive member to a recording medium, and a fixing means for fixing the toner image transferred onto the recording medium to the recording medium by heat and pressure.

[0100] [Methods for measuring various physical properties] The methods for measuring various physical properties are explained below.

[0101] <Separation of toner fine powder and toner particles from toner> Add 200 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a sucrose concentrate. Place 31 g of the sucrose concentrate and 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) in a centrifuge tube to prepare a dispersion. Add 1 g of toner to this dispersion and break up any clumps of toner with a spatula or similar.

[0102] The centrifuge tube is shaken in the shaker at 350 reciprocations per minute for 20 minutes. After shaking, the solution is transferred to a 50 mL glass tube for a swing rotor and centrifuged in a centrifuge at 3500 rpm for 30 minutes. After centrifugation, the top layer of the glass tube contains toner particles (including the toner fine powder adhering to the toner particle surface), while the lower aqueous layer contains the toner fine powder separated from the toner particles. The lower aqueous layer is sampled and centrifuged to separate the sucrose and toner fine powder, and the toner fine powder is collected. Centrifugation is repeated as necessary to thoroughly separate the dispersion, after which the dispersion is dried and the toner fine powder is collected.

[0103] When other external additives are used in combination, the fine powder for toner of the present disclosure can be selected using a centrifugal separation method or the like.

[0104] The fine powder for toner separated by the above method is used to measure the physical properties described below.

[0105] <Method for measuring the number average particle size of primary particles of fine powder for toner> The number-average particle size of the primary particles of fine powder for toner can be determined by centrifugal sedimentation. Specifically, 0.01 g of dried fine powder was placed in a 25 mL glass vial, and 0.2 g of 5% Triton solution and 19.8 g of RO water were added to prepare a solution. Next, the probe (the innermost tip) of an ultrasonic disperser was immersed in the solution, and ultrasonic dispersion was performed at an output of 20 W for 15 minutes to obtain a dispersion. Subsequently, the number-average particle size of the primary particles was measured using a CPS Instruments DC24000 centrifugal sedimentation particle size distribution analyzer. The disk rotation speed was set to 18,000 rpm, and the true density was 1.3 g / cm. 3 Before the measurement, the instrument was calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0106] <Method for obtaining particles after separating silicone oil> 10 g of toner fine powder is dispersed in 200 mL of hexane and subjected to ultrasonic treatment (frequency 30 kHz, output capacity 15 W, intensity 100%, time 5 minutes). After ultrasonic treatment, the dispersion is suction filtered, and the filtered material is collected and dried to obtain particles after silicone oil separation.

[0107] <Method for measuring the volume average diameter and average volume of particle pores> The volume average diameter and average volume of pores are measured by a gas adsorption method in which nitrogen gas is adsorbed onto the surface of a sample using a pore distribution analyzer Tristar 3000 (manufactured by Shimadzu Corporation). The measurement method follows the operating manual issued by Shimadzu Corporation.

[0108] First, approximately 0.5 g of sample is placed in a sample tube and vacuumed at 100°C for 24 hours. After vacuuming, the sample is weighed accurately to obtain a sample. From the obtained sample, the volume average diameter and the average volume in the pore diameter range of 1.7 nm to 300.0 nm can be determined by the BJH method using the pore size distribution measurement device described above. The density value required for measurement is the true density value measured using a dry density meter, Accupyc 1330 (Shimadzu Corporation).

[0109] <Solid 29 Analysis of silicon structure using Si-NMR> solid 29 When Si-NMR analysis is performed, peaks are detected in different shift regions depending on the structure of the functional group that binds to Si. By identifying the position of each peak using a standard sample, the structure that binds to Si can be identified. Furthermore, the abundance ratio of each structure can be calculated from the obtained peak area. The ratio of the peak area of ​​Q unit structure, T unit structure, D unit structure, and M unit structure to the total peak area can be calculated.

[0110] solid 29 The specific conditions for Si-NMR measurement are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DDMAS method 29Si 45° Sample tube: zirconia 3.2 mm diameter Sample: Filled in powder form into a test tube Sample rotation speed: 10kHz Relaxation delay: 180s Scan:2000

[0111] After the measurement, the peaks of the multiple silane components of the sample with different substituents and bonding groups are separated into the structures of formulas (1) to (4) by curve fitting, and the peak area of ​​each is calculated.

[0112] [ka] Formula (1): Q unit structure Formula (2): D unit structure Formula (3): M unit structure Formula (4): T unit structure

[0113] In the formulas (1) to (4), R1 to R6 represent alkyl groups having 1 to 6 carbon atoms. 29 Along with the Si-NMR measurement results 13 C-NMR and 1 The results of H-NMR measurements may also be used for identification.

[0114] <Method for measuring compression cohesion of fine powder for toner> The compression cohesion of toner fine powder is measured using a powder rheometer (FT4, Freeman Technology). First, 10 g of toner fine powder is weighed into a dedicated cylindrical split container, and the toner fine powder is compressed at the specified pressure (60 kPa) using a compression test piston attached to the main body. For 60 kPa samples, the powder is left in a dryer set to 100°C for at least one hour until immediately before measurement. The compressed fine powder layer is leveled off using the split part of the measurement container, and the upper part of the powder layer is removed. Next, a dedicated needle-shaped tool is attached to the main body and penetrated vertically into the powder layer. The compression cohesion can be obtained by measuring the penetration force at this time.

[0115] <Method for measuring the dynamic viscosity of silicone oil> The kinetic viscosity of the separated silicone oil is measured at 25°C using a fully automatic micro dynamic viscometer (manufactured by Viscotec Co., Ltd.).

[0116] <Method for measuring the number average molecular weight of silicone oil> The number-average molecular weight of the separated silicone oil is measured according to the usual method as follows. The sample is placed in tetrahydrofuran and the object to be measured and the tetrahydrofuran are thoroughly mixed while shaking. Next, the column is stabilized in a heat chamber at 40°C. Tetrahydrofuran is passed through the column at this temperature as a solvent at a flow rate of 1 mL per minute, and 10 μL of the GPC sample is injected to measure the number-average molecular weight of the object to be measured. A column manufactured by Tosoh Corporation (trade name: TSK gel Super HM-M) is used.

[0117] To measure number average molecular weight, a GPC chart is obtained by calculating the molecular weight distribution of the object being measured from the relationship between the logarithm of the calibration curve created using several monodisperse polystyrene standard samples and the count number. The standard polystyrene samples used to create the calibration curve are monodisperse polystyrenes manufactured by Aldrich with the following 10 molecular weights: 3500, 12000, 40000, 75000, 98000, 120000, 240000, 500000, 800000, and 1800000. An RI (refractive index) detector is used.

[0118] <Method for measuring the adhesion rate of toner fine powder to toner particles> (Water washing process) A 30 mL glass vial was filled with 20.7 g of sucrose (Kishida Chemical Co., Ltd.) dissolved in 10.3 g of ion-exchanged water and 6 mL of the surfactant Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) and mixed thoroughly to prepare a dispersion. The glass vial used was, for example, a VCV-30 (Nichiden Rika Glass Co., Ltd.) with an outer diameter of 35 mm and a height of 70 mm. 1.0 g of toner was added to the dispersion and allowed to settle naturally to prepare a pre-treatment dispersion. This pre-treatment dispersion was then shaken at 200 rpm for 5 minutes in a shaker (YS-8D model, Yayoi Corporation) to remove loosely adhered particles from the toner particle surface. The toner with the remaining tightly adhered particles was separated from the detached particles using a centrifuge. The centrifugation process was carried out at 3700 rpm for 30 minutes. The toner containing the remaining fine particles is collected by suction filtration, dried, and washed with water to obtain the toner.

[0119] (Method for measuring particle adhesion rate) The method for measuring the particle adhesion rate will be shown as an example. First, the fine particles contained in the toner particles before the water washing process are quantified. This is done by measuring the Si element intensity in the toner particles using a wavelength dispersive X-ray fluorescence analyzer Axios Advanced (manufactured by PANalytical). Next, the Si element intensity in the toner particles after the water washing process is measured in the same way. The adhesion rate (%) is calculated as follows: (Si element intensity in toner particles after water washing treatment / Si element intensity in toner particles before water washing treatment)×100 It can be calculated as follows.

[0120] [Configuration included in the embodiment of the present invention] The disclosure of this embodiment includes the following configuration. (Configuration 1) A fine powder for toner containing silicone oil, The silicone oil fractionated by the following fractionation method has the following composition, based on the number of all silicon atoms: (i) the ratio X1 (%) of the number of silicon atoms having the structure represented by the above formula (1) is 1% or more and 40% or less, (ii) the sum of the number ratio X2 (%) of silicon atoms having the structure represented by the formula (2) and the number ratio X3 (%) of silicon atoms having the structure represented by the formula (3) is 60% or more and 99% or less, the content of the separated silicone oil is 0.1% by mass or more and 10.0% by mass or less based on the mass of the fine powder for toner; A fine powder for toner characterized by: ·Preparative method: a) 10 g of fine powder for toner is dispersed in 200 mL of hexane, and subjected to ultrasonic treatment (frequency 30 kHz, output capacity 15 W, intensity 100%, time 5 minutes). b) After the ultrasonic treatment, the dispersion is filtered by suction. c) The hexane is distilled off from the filtrate to obtain silicone oil. (Configuration 2) The fine powder for toner according to Configuration 1, wherein, in the separated silicone oil, X1 (%) and X2 (%) satisfy the following formula: 1.0≦X2 / X1≦20.0 (Configuration 3) The fine powder for toner according to Configuration 1 or 2, wherein the number average molecular weight of the separated silicone oil is 300 or more and 3,000 or less. (Configuration 4) The kinetic viscosity of the separated silicone oil is 100 mm 2 / s or more 10000mm 2 4. The fine powder for toner according to any one of configurations 1 to 3, wherein the fine powder for toner has a viscosity of 1 / s or less. (Configuration 5) The particles obtained by drying the filtered residue obtained by the above-mentioned fractionation method are organosilicon polymer particles, 5. The fine powder for toner according to any one of configurations 1 to 4, wherein the organosilicon polymer particles have the structure of formula (1), formula (2), formula (3), or formula (4). (Configuration 6) With respect to the particles obtained by drying the filtered residue, when the ratio of the number of silicon atoms having the structure represented by formula (1) is Y1 (%) and the ratio of the number of silicon atoms having the structure represented by formula (2) is Y2 (%) based on the total number of silicon atoms contained in the particles obtained by drying the filtered residue, X1, X2, Y1, and Y2 are 0≦(Y2 / Y1) / (X2 / X1)≦3.0 The fine powder for toner according to configuration 5, which satisfies the above. (Configuration 7) The particles obtained by drying the filtered residue separated by the preparative method have pores, the volume average diameter of the pores is 5 nm or more and 20 nm or less, and the average volume of the pores is 0.3 cm 3 / g or more 1.0cm 3 7. The fine powder for toner according to any one of configurations 1 to 6, wherein the fine powder for toner has a molecular weight of 1 / g or less. (Configuration 8) The fine powder for toner according to any one of Configurations 1 to 7, wherein the number average particle diameter of the fine powder for toner is 80 nm or more and 150 nm or less. (Configuration 9) The particles obtained by drying the residue filtered out by the preparative method are composite microparticles having a base particle and a convex particle present on the surface of the base particle in a state where the convex particle is partially embedded, 9. The fine powder for toner according to any one of configurations 1 to 8, wherein the base particles contain an organosilicon polymer having any one of the structures of formula (1), (2), (3), or (4). (Configuration 10) The fine powder for toner according to any one of Configurations 1 to 9, wherein the fine powder for toner has a compression cohesion value of 100 mJ or more at 60 kPa. (Configuration 11) A toner comprising toner particles and fine powder adhering to or adhering to the surfaces of the toner particles, wherein the fine powder is the fine powder for toner according to any one of Configurations 1 to 10. (Configuration 12) The toner according to Configuration 11, wherein the content of the fine powder for toner is 0.1 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of the toner particles. (Configuration 13) The toner according to Configuration 11 or 12, wherein the adhesion rate of the fine powder for toner to the toner particles is 30% or more and 80% or less. [Example]

[0121] The present disclosure will be specifically explained with reference to the following examples. However, these examples are not intended to limit the present invention in any way. Unless otherwise specified, the "parts" in the following formulations are all based on mass.

[0122] <Production example of fine powder 1 for toner> 1. Hydrolysis and condensation polymerization process (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 12.2 g of dimethyldimethoxysilane were charged into a 500 mL beaker and stirred at 45° C. for 5 minutes. (2) To this was added 2.0 g of 28% ammonia water, 15.0 g of tetraethoxysilane, and 5.0 g of an aqueous dispersion of colloidal silica (solid silica content: 40% by mass, particle size: 30 nm) for forming convex particles, and the mixture was stirred at 30°C for 3.0 hours to obtain a raw material solution.

[0123] 2. Particulate process 120.0 g of RO water was placed in a 1000 mL beaker, and the raw material solution obtained in step 1 above was added dropwise over 5 minutes while stirring at 25°C. The mixture was then heated to 60°C and stirred for 1.5 hours while maintaining the temperature at 60°C, yielding a dispersion of fine powder.

[0124] 3. Surface treatment process To the dispersion of the fine powder obtained in step 2 above, 6.0 g of dimethyldimethoxysilane, 5.0 g of tetraethoxysilane, and 4.0 g of hexamethyldisilazane were added and stirred at 60°C for 1.5 hours. After leaving to stand for 5 minutes, the powder that settled at the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain fine powder for toner 1. The physical properties of the obtained fine powder for toner 1 are shown in Tables 1-1 and 1-2.

[0125] <Production example of fine powder 2 for toner> Fine powder for toner 2 was obtained in the same manner as in the production example for fine powder for toner 1, except that hexamethyldisilazane was not added and 7.5 g of dimethyldimethoxysilane, 1.5 g of trimethoxymethylsilane, and 3.0 g of tetraethoxysilane were added in the surface treatment step. The physical properties of the obtained fine powder for toner 2 are shown in Tables 1-1 and 1-2.

[0126] <Production example of fine powder 3 for toner> Fine powder for toner 3 was obtained in the same manner as in the production example for fine powder for toner 1, except that in (1) of the hydrolysis and condensation polymerization step, dimethyldimethoxysilane was changed to 4.2 g, in (2) tetraethoxysilane was changed to 23 g, and in the surface treatment step, dimethyldimethoxysilane was changed to 3.0 g, tetraethoxysilane to 2.5 g, and hexamethyldisilazane to 2.0 g. The physical properties of the obtained fine powder for toner 3 are shown in Tables 1-1 and 1-2.

[0127] <Production example of fine powder 4 for toner> Except for changing the stirring time to 1.0 hour in the surface treatment step, the same procedure as in the production example of fine powder for toner 3 was carried out to obtain fine powder for toner 4. The physical properties of the obtained fine powder for toner 4 are shown in Tables 1-1 and 1-2.

[0128] <Production example of fine powder 5 for toner> Fine powder for toner 5 was obtained in the same manner as in the production example of fine powder for toner 1, except that the colloidal silica aqueous dispersion was not added in the hydrolysis and polycondensation step (2). The physical properties of the obtained fine powder for toner 5 are shown in Tables 1-1 and 1-2.

[0129] <Production example of fine powder 6 for toner> Fine powder for toner 6 was obtained in the same manner as in the production example of fine powder for toner 5, except that the stirring time was changed to 3.5 hours in the hydrolysis and polycondensation step (2). The physical properties of the obtained fine powder for toner 6 are shown in Tables 1-1 and 1-2.

[0130] <Production example of fine powder 7 for toner> Fine powder for toner 7 was obtained in the same manner as in the production example of fine powder for toner 5, except that the stirring time was changed to 2.5 hours in the hydrolysis and polycondensation step (2). The physical properties of the obtained fine powder for toner 7 are shown in Tables 1-1 and 1-2.

[0131] <Production example of fine powder 8 for toner> Fine powder for toner 8 was obtained in the same manner as in the production example of fine powder for toner 5, except that the stirring time was changed to 4.0 hours in the hydrolysis and polycondensation step (2). The physical properties of the obtained fine powder for toner 8 are shown in Tables 1-1 and 1-2.

[0132] <Production example of fine powder 9 for toner> Fine powder for toner 9 was obtained in the same manner as in the production example of fine powder for toner 5, except that the stirring time was changed to 2.0 hours in the hydrolysis and polycondensation step (2). The physical properties of the obtained fine powder for toner 9 are shown in Tables 1-1 and 1-2.

[0133] <Production example of fine powder 10 for toner> Fine powder for toner 10 was obtained in the same manner as in the production example of fine powder for toner 5, except that in the hydrolysis and polycondensation step (2), 28% aqueous ammonia was used in place of 2.5 g. The physical properties of the obtained fine powder for toner 10 are shown in Tables 1-1 and 1-2.

[0134] <Production example of fine powder 11 for toner> Fine powder for toner 11 was obtained in the same manner as in the production example of fine powder for toner 5, except that in the hydrolysis and polycondensation step (2), 28% aqueous ammonia was used in place of 1.5 g. The physical properties of the obtained fine powder for toner 11 are shown in Tables 1-1 and 1-2.

[0135] <Production example of fine powder 12 for toner> Fine powder for toner 12 was obtained in the same manner as in the production example of fine powder for toner 10, except that in the hydrolysis and polycondensation step (1), the temperature was changed to 50° C. The physical properties of the obtained fine powder for toner 12 are shown in Tables 1-1 and 1-2.

[0136] <Production example of fine powder 13 for toner> Fine powder for toner 13 was obtained in the same manner as in the production example of fine powder for toner 11, except that in the hydrolysis and polycondensation step (1), the temperature was changed to 40° C. The physical properties of the obtained fine powder for toner 13 are shown in Tables 1-1 and 1-2.

[0137] <Production example of fine powder 14 for toner> A 2000 mL beaker was charged with 124.0 g of ethanol, 24.0 g of RO water, and 10.0 g of 28% aqueous ammonia. The solution was adjusted to 70°C, and 232.0 g of tetraethoxysilane and 84.0 g of 5.4% aqueous ammonia were added dropwise over 0.5 hours with stirring. After the addition was completed, stirring was continued for another 0.5 hours to carry out hydrolysis, yielding a dispersion of silica particles.

[0138] To the dispersion of silica particles obtained in the above step, 70.0 g of dimethyldimethoxysilane and 15.0 g of tetraethoxysilane were added at room temperature, and then the dispersion was heated to 50 to 60°C and stirred for 1.5 hours. The powder in the dispersion was recovered by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain fine powder for toner 14. The physical properties of the obtained fine powder for toner 14 are shown in Tables 1-1 and 1-2.

[0139] <Production example of fine powder 15 for toner> Fine powder for toner 15 was obtained in the same manner as in the production example for fine powder for toner 5, except that hexamethyldisilazane was not added and 13.5 g of dimethyldimethoxysilane and 2.0 g of tetraethoxysilane were added in the surface treatment step. The physical properties of the obtained fine powder for toner 15 are shown in Tables 1-1 and 1-2.

[0140] <Production example of fine powder 16 for toner> Fine powder for toner 16 was obtained in the same manner as in Production Example 5 for fine powder for toner, except that hexamethyldisilazane was not added and 8.0 g of dimethyldimethoxysilane, 7.0 g of tetraethoxysilane, and 0.5 g of 28% aqueous ammonia were added in the surface treatment step. The physical properties of the obtained fine powder for toner 16 are shown in Tables 1-1 and 1-2.

[0141] <Production example of fine powder 17 for toner> Fine powder for toner 17 was obtained in the same manner as in the production example for fine powder for toner 5, except that in the surface treatment step, the amounts of dimethyldimethoxysilane, tetraethoxysilane, and hexamethyldisilazane were changed to 4.0 g, 6.0 g, and 5.0 g, respectively, and the reaction temperature was changed to 50° C. The physical properties of the obtained fine powder for toner 17 are shown in Tables 1-1 and 1-2.

[0142] <Production example of fine powder 18 for toner> Fine powder for toner 18 was obtained in the same manner as in the production example of fine powder for toner 5, except that hexamethyldisilazane was not added and 14.0 g of dimethyldimethoxysilane and 1.0 g of tetraethoxysilane were added in the surface treatment step. The physical properties of the obtained fine powder for toner 18 are shown in Tables 1-1 and 1-2.

[0143] <Production example of fine powder 19 for toner> A 2000 mL beaker was charged with 124.0 g of ethanol, 24.0 g of RO water, and 10.0 g of 28% aqueous ammonia. The temperature of the solution was adjusted to 70°C, and 232.0 g of tetraethoxysilane and 84.0 g of 5.4% aqueous ammonia were added dropwise over 0.5 hours with stirring. After the addition was completed, stirring was continued for another 0.5 hours to allow hydrolysis to occur, resulting in a dispersion of silica particles. The dispersion was heated to 50-60°C and stirred for 1.5 hours. The powder in the dispersion was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain fine powder for toner 19. The physical properties of the resulting fine powder for toner 19 are shown in Tables 1-1 and 1-2.

[0144] <Production example of fine powder 20 for toner> In the surface treatment process, hexamethyldisilazane is not added, and the 2 Fine powder for toner 20 was obtained in the same manner as in the production example of fine powder for toner 1, except that 3.0 g of dimethyl silicone oil at 1 / s was added. The physical properties of the obtained fine powder for toner 20 are shown in Tables 1-1 and 1-2.

[0145] <Production example of fine powder 21 for toner> Fine powder for toner 21 was obtained in the same manner as in Production Example 1 of fine powder for toner 1, except that in the surface treatment step, the amounts of dimethyldimethoxysilane, tetraethoxysilane, and hexamethyldisilazane were changed to 18.0 g, 15.0 g, and 12.0 g, and the stirring time was changed to 2.0 hours. The physical properties of the obtained fine powder for toner 21 are shown in Tables 1-1 and 1-2.

[0146] <Production example of fine powder 22 for toner> Fine powder for toner 22 was obtained in the same manner as in the production example of fine powder for toner 14, except that tetraethoxysilane was not added to the dispersion of silica particles, and 12.0 g of dimethyldimethoxysilane and 3.0 g of trimethoxymethylsilane were added. The physical properties of the obtained fine powder for toner 22 are shown in Tables 1-1 and 1-2.

[0147] [Table 1-1]

[0148] [Table 1-2]

[0149] <Production Example of Polyester Resin A1> Polyoxypropylene (2,2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 mole parts) Terephthalic acid (TPA) 25.0 parts (0.145 mole parts) Adipic acid 8.0 parts (0.054 moles) Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then purged with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 4 hours at 200°C while stirring (first reaction step). Then, 1.2 parts (0.006 moles) of trimellitic anhydride (TMA) was added, and the mixture was allowed to react for 1 hour at 180°C (second reaction step), yielding polyester resin A1, the binder resin component. The acid value of this polyester resin A1 was 5 mgKOH / g.

[0150] <Production Example of Polyester Resin A2> Polyoxypropylene (2,2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts (0.155 moles) Terephthalic acid 24.1 parts (0.145 mole parts) Titanium tetrabutoxide 0.6 parts The above materials were placed in a 4L four-neck glass flask, fitted with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then purged with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 2 hours at 200°C while stirring. Subsequently, 5.8 parts (0.030 moles) of trimellitic anhydride was added, and the mixture was allowed to react for 10 hours at 180°C, yielding polyester resin A2. The acid value of this polyester resin A2 was 10 mgKOH / g.

[0151] <Production Example of Toner Particle 1> Polyester resin A1 70.0 parts Polyester resin A2 30.0 parts Fischer-Tropsch wax (maximum endothermic peak temperature 78°C) 5.0 parts CI Pigment Blue 15:3 5.0 parts 0.1 parts of 3,5-di-t-butylsalicylic acid aluminum compound The raw materials shown in the above recipe were mixed in a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a rotation speed of 20 s -1After mixing for 5 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 125°C and a rotation speed of 300 rpm. The resulting kneaded mixture was cooled and coarsely pulverized using a hammer mill to obtain a coarsely pulverized product with a diameter of 1 mm or less. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Corporation). Further, classification was carried out using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were a classification rotor rotation speed of 50.0 s -1 The resulting toner particles 1 had a weight average particle size (D4) of 5.9 μm.

[0152] <Toner 1 manufacturing example> 100 parts of toner particles 6.0 parts of fine powder for toner 1 The above materials were mixed in a Henschel mixer FM-10C (Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 30 s -1 The mixture was mixed for a rotation time of 10 minutes to obtain toner particle mixture 1.

[0153] (Heat treatment process) The obtained toner particle mixture 1 was subjected to heat treatment using the surface treatment device shown in FIG. 1 to obtain toner 1. The physical properties of toner 1 are shown in Table 2. The operating conditions for the heat treatment were a feed rate of 2 kg / hr, a hot air temperature of 150°C, and a hot air flow rate of 6 m 3 / min., cold air temperature = -5℃, cold air flow rate = 2.5m 3 / min., Blower air volume = 11m 3 / min., injection air flow rate = 1m 3 / min.

[0154] <Toner 2-26 Manufacturing Example> Toners 2 to 26 were obtained in the same manner as in the production example of Toner 1, except that the type of fine powder for toner, whether or not a heat treatment step was performed, and the hot air temperature in the heat treatment step were changed to those shown in Table 2. The adhesion rates of the fine powder for toner in Toners 2 to 26 are shown in Table 2.

[0155] [Table 2]

[0156] <Carrier 1 manufacturing example> Number average particle size: 0.30 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite 1 Number average particle size: 0.50 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) magnetite2 To each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles. Phenol: 10% by weight Formaldehyde solution: 6% by mass (40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water) Magnetite treated with the above silane compound 1:58 mass% Magnetite treated with the above silane compound 2: 26 mass% The above materials, 5 parts of a 28% by weight aqueous ammonia solution, and 20 parts of water were placed in a flask, and the temperature was raised to 85°C over 30 minutes while stirring and mixing, and the temperature was maintained at 85°C for 30 minutes. The polymerization reaction was carried out for 3 hours, and the resulting phenolic resin was cured. The cured phenolic resin was then cooled to 30°C, and more water was added. The supernatant was removed, and the precipitate was washed with water and air-dried. This was then dried at 60°C under reduced pressure (5 mmHg or less) to obtain magnetic material-dispersed spherical carrier 1. The volume-based 50% particle size (D50) was 34.2 μm.

[0157] <Production examples of two-component developers 1 to 26> To 92.0 parts of carrier 1, 8.0 parts of toners 1 to 26 were added and mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain two-component developers 1 to 26.

[0158] Example 1 <Toner evaluation method> The image forming apparatus used was a modified Canon imagePRESS C810 digital commercial printing printer, with two-component developer 1 loaded into the cyan developer unit. The apparatus was modified so that the fixing temperature, process speed, developer carrier DC voltage VDC, electrostatic latent image carrier charging voltage VD, and laser power could be freely set. Image output evaluation was performed by outputting an FFh image (solid image) with the desired image ratio, and adjusting VDC, VD, and laser power so that the toner coverage on the FFh image on the paper was as desired, and then evaluating as described below.

[0159] FFh is a value that represents 256 gradations in hexadecimal, with 00h being the first gradation of the 256 gradations (white background) and FFh being the 256th gradation of the 256 gradations (solid area).

[0160] The evaluation was carried out based on the following evaluation methods, and the results are shown in Table 3.

[0161] [Cleaning performance evaluation] ·Paper: CS-680 (68.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner coverage on paper: 0.35mg / cm 2 (FFh image) (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: A ruled chart with an image ratio of 30% on the entire surface of the A4 paper mentioned above Test environment: High temperature and humidity (temperature 30°C / humidity 80% RH (hereinafter referred to as H / H)) Process speed: 450mm / sec The above evaluation image was output on 100,000 sheets, and the cleaning ability was evaluated. When cleaning failure occurred, vertical streak-like stains appeared on the surface of the charging roller and on the paper. Visual evaluation of this state was used as an evaluation index for cleaning ability. (Evaluation criteria) A: No vertical streaks on the paper, no dirt on the charging roller B: No vertical streaks on paper, dirty charging roller C: One vertical streak occurs on the paper D: Two vertical streaks on the paper E: Vertical streaks appear in three places on the paper F: Four vertical streaks on the paper G: Vertical streaks appear in five places on the paper H: Vertical streaks occur in six or more places on the paper

[0162] [Developability evaluation] ·Paper: GF-C081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.45mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: 2mm wide strips of solid area and 18mm wide strips of white area are arranged repeatedly in a direction parallel to the paper feed direction of the A4 paper. Test environment: room temperature and low humidity environment (23°C / 5%RH). After printing the pattern image on 10,000 sheets, printing was stopped for a while, and then an image in which the entire surface of the paper was halftone (80h) was printed.

[0163] For a full solid image, the image density was measured at 20 random locations using an X-Rite color reflection densitometer ("500 Series," manufactured by X-Rite), and the evaluation was based on the difference between the maximum and minimum image density values ​​(image density difference). Note that density changes are likely to occur if silicone oil migrates from the toner fine powder to the component, causing contamination of the component. (Evaluation criteria) A: Image density difference is less than 0.02 B: Image density difference is 0.02 or more and less than 0.04 C: Image density difference is 0.04 or more and less than 0.06 D: Image density difference is 0.06 or more and less than 0.08 E: Image density difference is 0.08 or more and less than 0.10 F: Image density difference is 0.10 or more and less than 0.12 G: Image density difference is 0.12 or more

[0164] [Examples 2 to 22, Comparative Examples 1 to 4] Instead of the two-component developer 1, two-component developers 2 to 26 were used and evaluation was carried out in the same manner as in Example 1. The evaluation results of Examples 2 to 22 and Comparative Examples 1 to 4 are shown in Table 3.

[0165] [Table 3]

Claims

1. A toner fine powder containing silicone oil, The silicone oil fractionated by the following fractionation method has the following composition, based on the number of all silicon atoms: (i) the ratio X1 (%) of the number of silicon atoms having the structure represented by formula (1) is 1% or more and 40% or less, (ii) the sum of the number ratio X2 (%) of silicon atoms having a structure represented by formula (2) and the number ratio X3 (%) of silicon atoms having a structure represented by formula (3) is 60% or more and 99% or less; the content of the separated silicone oil is 0.1% by mass or more and 10.0% by mass or less based on the mass of the fine powder for toner; A fine powder for toner characterized by: ・Preparative method: a) 10 g of fine powder for toner is dispersed in 200 mL of hexane, and subjected to ultrasonic treatment (frequency 30 kHz, output capacity 15 W, intensity 100%, time 5 minutes). b) After the ultrasonic treatment, the dispersion is subjected to suction filtration. c) The hexane is distilled off from the filtrate to obtain a silicone oil. 【Chemistry 1】 (R 1 , R 2 , R 4 ~R 6 each independently represents an alkyl group having 1 to 6 carbon atoms.

2. 2. The fine powder for toner according to claim 1, wherein in the separated silicone oil, X1 (%) and X2 (%) satisfy the following formula: 1.0≦X2 / X1≦20.0

3. 3. The fine powder for toner according to claim 1, wherein the number average molecular weight of the separated silicone oil is 300 or more and 3,000 or less.

4. The kinetic viscosity of the collected silicone oil is 100 mm 2 / s or more 10000mm 2 3. The fine powder for toner according to claim 1, wherein the average particle size is 1 / s or less.

5. the particles obtained by drying the residue separated by filtration in the fractionation method are organosilicon polymer particles, 3. The fine powder for toner according to claim 1, wherein the organosilicon polymer particles have a structure represented by the following formula (1), (2), (3), or (4): 【Chemistry 2】 (R 1 ~R 6 each independently represents an alkyl group having 1 to 6 carbon atoms.

6. With respect to the particles obtained by drying the filtered residue, when the ratio of the number of silicon atoms having the structure represented by formula (1) is Y1 (%) and the ratio of the number of silicon atoms having the structure represented by formula (2) is Y2 (%) based on the total number of silicon atoms contained in the particles obtained by drying the filtered residue, X1, X2, Y1, and Y2 are 0≦(Y2 / Y1) / (X2 / X1)≦3.0 6. The fine powder for toner according to claim 5, which satisfies the above formula:

7. The particles obtained by drying the residue filtered by the preparative method have pores, the volume average diameter of the pores is 5 nm or more and 20 nm or less, and the average volume of the pores is 0.3 cm 3 / g or more 1.0cm 3 3. The fine powder for toner according to claim 1, wherein the molecular weight is 1 / g or less.

8. 3. The fine powder for toner according to claim 1, wherein the number average particle diameter of said fine powder for toner is 80 nm or more and 150 nm or less.

9. The particles obtained by drying the residue filtered out by the fractionation method are composite fine particles having a base particle and a convex particle present on the surface of the base particle in a state where the convex particle is partially buried, 3. The toner fine powder according to claim 1, wherein the base particles contain an organosilicon polymer having any of the following structures: (1), (2), (3), and (4). 【Transformation 3】 (R 1 ~R 6 each independently represents an alkyl group having 1 to 6 carbon atoms.

10. 3. The fine powder for toner according to claim 1, wherein the fine powder for toner has a compression cohesion value of 100 mJ or more at 60 kPa.

11. 3. A toner comprising toner particles and fine powder adhering to or adhering to the surfaces of said toner particles, said fine powder being the fine powder for toner according to claim 1 or 2.

12. 12. The toner according to claim 11, wherein the content of the fine powder for toner is 0.1 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

13. 12. The toner according to claim 11, wherein the adhesion rate of the fine powder for toner to the toner particles is 30% or more and 80% or less.

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