CN116610012A

CN116610012A - Fine particles containing silicon and toner

Info

Publication number: CN116610012A
Application number: CN202310117799.1A
Authority: CN
Inventors: 菅野伊知朗; 井田隼人; 渡边裕树; 冠木麻里
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 2022-02-16
Filing date: 2023-02-15
Publication date: 2023-08-18

Abstract

The present invention relates to fine particles containing silicon and a toner. The invention provides fine particles containing silicon, wherein the number average particle diameter of primary particles of the fine particles is 0.05 [ mu ] m or more and 0.20 [ mu ] m or less, and wherein the fine particles contain silicon atoms in a proportion of 20% or more relative to all elements in measurement by X-ray fluorescence.

Description

Fine particles containing silicon and toner

Technical Field

The present invention relates to fine particles containing silicon and a toner to be used in an electrophotographic system.

Background

In recent years, with the widespread use of electrophotographic full-color copiers, there is an increasing demand for toners for electrophotography to respond to an increase in printing speed and to have environmental stability and longer life.

Generally, silica has been widely known as an external additive used in toners so far, and an example in which silica obtained by a dry method or a wet method (sol-gel method) is subjected to surface treatment to improve the hydrophobicity thereof has been reported. For example, in japanese patent application laid-open No.2007-99582, an example is disclosed in which spherical sol-gel silica fine particles of high hydrophobicity are added to toner base particles to improve the charging stability of toner.

Further, in Japanese patent application laid-open No.2016-138035, an example of suppressing discoloration and concentration unevenness by using silicon dioxide particles treated with silicone oil is disclosed.

Further, in japanese patent No.6116711, an example is disclosed in which polyalkylsilsesquioxane fine particles are added to toner base particles to improve fluidity and charging stability of the toner.

The silica particles of the prior art have high chargeability and are liable to cause uneven charge distribution on the toner surface when externally added to the toner. For this reason, when an image is output on an embossed paper or matte paper having large irregularities on the surface of the paper, the transferability of the toner is insufficient, and density unevenness may occur. Further, under the condition that a great stress is applied to the toner, for example, when a large number of low-printing-rate images are output, the hue of the images may fluctuate. Therefore, there is still room for improvement from the viewpoints of charging stability and durability stability of the toner (Japanese patent application laid-open No.2007-99582 and Japanese patent application laid-open No. 2016-138035). Further, when an image is output for a long period of time, an external additive present on the toner surface may be transferred to a carrier or a member within the body of the image output apparatus, and cause an image defect (japanese patent No. 6116711). Further, when the toner in the developing machine is frequently replaced, for example, when a large number of high-print-rate images are output, particularly the effect becomes strong.

As described above, in the related art, in the case of outputting an image by using paper having large irregularities or in the case of outputting a large amount of high-print-rate images, there is room for improvement from the viewpoints of charging stability and durability stability of external additives.

Disclosure of Invention

An object of the present invention is to provide fine particles and toner solving the above problems. In particular, the present invention aims to improve charging stability and endurance stability of toner and reduce member contamination, thereby stably obtaining high-quality images over a long period of time.

The present invention relates to fine particles containing silicon, wherein the number average particle diameter of primary particles of the fine particles is 0.05 μm or more and 0.20 μm or less, wherein in measurement by means of X-ray fluorescence (XRF), the fine particles contain silicon atoms in a proportion of 20% or more with respect to all elements, and wherein, regarding the proportion of silicon atoms measured in the case where the fine particles are etched by irradiation with Ar-K alpha rays in analysis by means of X-ray photoelectron spectroscopy (XPS), when the proportion of silicon atoms having the following structure (a) is represented by X and the sum of the proportions of silicon atoms having the following structures (b) to (d) is represented by Y,

(i) Always satisfies the relation of X < Y in the measurement range of the following condition A, and

(ii) Within the measurement range of the following condition B, there is a point where the relationship of X < Y changes to the relationship of X > Y, and the relationship of X > Y is satisfied all the time after the change:

condition a: a time period starting from a time required for cutting a test piece made of PET to a depth of 2nm by irradiation with Ar-K alpha rays and ending with a time required for cutting the test piece to a depth of 20 nm;

condition B: a time period starting from a time required for cutting a test piece made of PET to a depth of 20nm by irradiation with Ar-ka radiation and ending with a time required for cutting the test piece to a depth of 50 nm.

Wherein R is ₁ 、R ₂ And R is ₃ Each independently represents a hydrocarbon group having 1 to 6 carbon atoms.

The present invention also relates to a toner including toner particles and fine particles, wherein the fine particles are fine particles having the above-described constitution.

Further features of the invention will become apparent from the following description of exemplary embodiments with reference to the attached drawings.

Drawings

Fig. 1 is an explanatory diagram of a heat treatment apparatus suitable for controlling the fixation rate of fine particles to toner particles.

Detailed Description

In the present invention, unless otherwise specified, the description of the numerical ranges "Σand xx or below" or "Σto×" means a numerical range including a lower limit and an upper limit as endpoints.

The inventors of the present invention consider that the mechanism that exhibits the effects of the present invention is as follows.

Representative silica particles used so far as external additives for toner are particles each containing a siloxane bond as a main component. Silica particles have high chargeability and are liable to cause uneven charge distribution on the toner surface. Furthermore, the polyalkylsilsesquioxane particles of the related art can achieve uniform charge distribution on the toner surface, but the polyalkylsilsesquioxane particles are liable to deform due to a low young's modulus and may be detached from the toner particles when subjected to stress from a member such as a carrier in a developing unit.

The present inventors have conducted intensive studies and as a result, have found that the above-described problems can be solved when the structures of the surface layer of fine particles and the interior of fine particles are optimized. Thus, the present invention has been achieved. Although the mechanism thereof is not clear, it is considered that when an alkyl group is introduced in a large amount into the surface layer of fine particles, the charge distribution on the surface of the toner becomes uniform and the flying property of the toner is improved to improve the transferability. Further, it is presumed that when fine particles have an appropriate hardness by introducing a large amount of siloxane bonds into the inside of the fine particles, stress from the outside can be relaxed to improve the fixation of the fine particles to toner particles, thereby suppressing transfer to the member, and the durability stability of the toner can be improved.

[ Fine particles ]

The fine particles of the present invention are fine particles containing silicon, wherein the number average particle diameter of primary particles of the fine particles is 0.05 μm or more and 0.20 μm or less, wherein in measurement by means of X-ray fluorescence (XRF), the fine particles contain silicon atoms in a proportion of 20% or more with respect to all elements, and wherein, regarding the proportion of silicon atoms measured in the case where the fine particles are etched by irradiation with Ar-ka rays in analysis by means of X-ray photoelectron spectroscopy (XPS), when the proportion of silicon atoms having the following structure (a) is represented by X and the sum of the proportions of silicon atoms having the following structures (b) to (d) is represented by Y,

condition a: a period of time starting from a time required for cutting a test piece (made of polyethylene terephthalate resin) made of PET to a depth of 2nm by irradiation with Ar-ka radiation and ending with a time required for cutting the test piece to a depth of 20 nm;

condition B: a period of time starting from a time required for cutting a test piece made of PET to a depth of 20nm by irradiation with Ar-ka radiation and ending with a time required for cutting the test piece to a depth of 50 nm:

Wherein R is ₁ 、R ₂ And R is ₃ Each independently represents a hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbyl group is preferably an alkyl group.

In the measurement range of the condition a, when X and Y do not always satisfy the relationship of X < Y, the charging on the surface of the fine particles becomes too high, and thus the effect of improving the transferability cannot be obtained. Further, when there is no point in the measurement range of the condition B where X and Y change from the relationship of X < Y to the relationship of X > Y, or when there is a change point in the measurement range of the condition B but the relationship of X > Y is not always satisfied after the change, the fine particles become too soft, and thus may be detached from the toner due to the stress to which the toner is subjected from the member. Therefore, contamination of the member by fine particles cannot be suppressed, and a high-quality image cannot be obtained. The relationship between X and Y can be controlled by hydrolysis and condensation conditions (reaction temperature, reaction time, stirring time), pH, kind of catalyst, and further ratio of monomers to be added and addition order of monomers at the time of reaction in the wet production method.

For example, the relationship of X < Y within the measurement range of the condition a is always satisfied by a method involving increasing the mixing ratio of the bifunctional silane monomer having the structure (c), a method involving gradually adding the bifunctional silane monomer having the structure (c) later, a method involving raising the pH of the solution, or the like. The relationship of X > Y within the measurement range of the condition B is always satisfied by a method involving increasing the mixing ratio of the tetrafunctional silane monomer having the structure (a), a method involving increasing the temperature in the hydrolysis step, or the like.

The method for producing fine particles is not particularly limited, but it is preferable to form particles by hydrolysis and polycondensation of a silicon compound (silane monomer) by a sol-gel method. Specifically, it is preferable to form particles by polymerizing a mixture of a difunctional silane having 2 siloxane bonds and a tetrafunctional silane having 4 siloxane bonds by means of hydrolysis and polycondensation reactions. Silane monomers such as difunctional silanes and tetrafunctional silanes are described subsequently.

Specifically, it is preferable that the fine particles are polycondensates of at least one silicon compound selected from the group consisting of difunctional silanes and at least one silicon compound selected from the group consisting of tetrafunctional silanes. The proportion of the bifunctional silane is preferably 30mol% or more and 70mol% or less, more preferably 40mol% or more and 60mol% or less. The proportion of the tetrafunctional silane is preferably 30mol% or more and 80mol% or less, more preferably 40mol% or more and 70mol% or less.

The fine particles of the present invention include particles of a silicon polymer having a siloxane bond. The particles of the silicon polymer contain the silicon polymer in an amount of preferably 90% by mass or more, more preferably 95% by mass or more.

The method of producing the silicon polymer particles is not particularly limited, and the silicon polymer particles can be obtained, for example, by: the silane compound is added dropwise to water, the resultant is subjected to hydrolysis and condensation reaction with a catalyst, and then the resultant suspension is filtered and dried. The particle diameter of the silicon polymer particles can be controlled by the kind of catalyst, the compounding ratio, the reaction start temperature, the dropping time, and the like. Examples of catalysts include, but are not limited to: acidic catalysts such as hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid; and basic catalysts such as ammonia, sodium hydroxide, and potassium hydroxide.

Preferably, the silicon polymer particles are produced by the following method. Specifically, it is preferable that the method comprises: a first step of obtaining a hydrolysate of a silicon compound; a second step of mixing the hydrolysate with an alkaline aqueous medium to cause the hydrolysate to undergo polycondensation reaction; and a third step of mixing and granulating the polycondensation reaction product with the aqueous solution. In some cases, the hydrophobized spherical silicon polymer particles may be obtained by further compounding a hydrophobizing agent into the spherical silicon polymer particle dispersion.

In the first step, in an aqueous solution in which an acidic or basic substance used as a catalyst is dissolved in water, a silicon compound and the catalyst are brought into contact with each other by a method such as stirring or mixing. As the catalyst, a known catalyst can be suitably used. Specific examples of the catalyst include: acidic catalysts such as acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid; and basic catalysts such as ammonia, sodium hydroxide, and potassium hydroxide.

The amount of the catalyst to be used may be appropriately adjusted depending on the kind of the silicon compound and the catalyst. The amount to be used is preferably 1X 10 with respect to 100 parts by mass of water for hydrolysis of the silicon compound ^-3 The mass part is selected in a range of 1 mass part or more and 1 mass part or less.

When the catalyst is used in an amount of 1X 10 ^-3 When the amount is equal to or more than the above parts by mass, the reaction proceeds sufficiently. Meanwhile, when the amount of the catalyst used is 1 part by mass or less, the concentration of the catalyst remaining as an impurity in the fine particles becomes low, and hydrolysis can be easily performed. The amount of water to be used is relative to 1mol of silicon compoundPreferably 2mol or more and 15mol or less. When the amount of water is 2mol or more, the hydrolysis reaction proceeds sufficiently. When the amount of water is 15mol or less, productivity is improved.

The reaction temperature is not particularly limited, and the reaction may be performed at ordinary temperature or in a heated state. However, it is preferable to carry out the reaction in a state where the temperature is kept at 10 to 60 ℃, because the hydrolysate is obtained in a short time and the partial condensation reaction of the produced hydrolysate can be suppressed. The reaction time is not particularly limited and may be appropriately selected in consideration of the reactivity of the silicon compound to be used, the composition of the reaction liquid prepared by compounding the silicon compound with acid and water, and the productivity.

In the method for producing silicon polymer particles, as a second step, the raw material solution obtained in the first step is mixed with an alkaline aqueous medium to subject the particle precursor to polycondensation reaction. Thus, a polycondensation reaction liquid was obtained. Here, the alkaline aqueous medium is a liquid obtained by mixing an alkali component, water, an organic solvent or the like as required.

The alkali component used in the alkaline aqueous medium is an alkali component that exhibits alkalinity in an aqueous solution and serves as a neutralizing agent for the catalyst used in the first process and as a catalyst for the polycondensation reaction in the second process. Examples of such base components may include: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine.

The amount of the base component used is an amount that allows the base component to neutralize the acid and effectively act as a catalyst for the polycondensation reaction. For example, when ammonia is used as the base component, the amount thereof to be used is generally selected in the range of 0.01 parts by mass or more and 12.5 parts by mass or less with respect to 100 parts by mass of the mixture of water and the organic solvent.

In the second step, in order to prepare an alkaline aqueous medium, an organic solvent may be further used in addition to the alkali component and water. The organic solvent is not particularly limited as long as the organic solvent has compatibility with water, and an organic solvent dissolving 10g or more of water per 100g at normal temperature and normal pressure is suitable.

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

Among the above-listed organic solvents, alcohol-based solvents such as methanol, ethanol, 2-propanol and butanol are preferable. Further, from the viewpoints of hydrolysis and dehydration condensation reaction, it is more preferable to select the same alcohol as the alcohol to be produced as the elimination product as the organic solvent.

In the third step, the polycondensation reaction product obtained in the second step and the aqueous solution are mixed and then granulated. As the aqueous solution, water (for example, tap water or pure water) may be suitably used, but a component exhibiting compatibility with water, such as a salt, an acid, an alkali, an organic solvent, a surfactant, or a water-soluble polymer, may be further added to water. The respective temperatures of the polycondensation reaction liquid and the aqueous solution at the time of mixing are not particularly limited, and are preferably selected in the range of 5 ℃ to 70 ℃ in view of the composition, productivity and the like thereof.

As a method for recovering the silicon polymer particles, known methods may be used without any particular limitation. For example, methods and filtration methods involving scooping out the floating powder are presented. Among them, the filtration method is preferable because of its simple operation. The filtration method is not particularly limited, and any known device for vacuum filtration, centrifugal filtration, pressure filtration, or the like may be selected. The filter paper, filter cloth, and the like for filtration are not particularly limited as long as they are industrially available, and may be appropriately selected according to the apparatus to be used.

The monomer to be used may be appropriately selected depending on, for example, compatibility with the solvent and the catalyst or hydrolyzability. Examples of tetrafunctional silane monomers capable of incorporation into structure (a) include tetramethoxysilane, tetraethoxysilane and tetraisocyanatosilane. Among them, tetraethoxysilane is preferable.

Examples of trifunctional silane monomers capable of incorporating structure (b) include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methyltrimethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methyltrimethoxychlorosilane, methyltriethoxysilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrimethoxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, trihexyltrimethoxysilane, triethoxysilane, phenyltriethoxysilane, and triethylphenyltrimethoxysilane. Among them, methyltrimethoxysilane is preferable.

Examples of difunctional silane monomers capable of incorporating structure (c) include di-tert-butyldichlorosilane, di-tert-butyldimethoxy silane, di-tert-butyldiethoxy silane, dibutyl dichloro silane, dibutyl dimethoxy silane, dibutyl diethoxy silane, dichlorodecyl methyl silane, dimethoxy decyl methyl silane, diethoxy decyl methyl silane, dichloro dimethyl silane, dimethoxy dimethyl silane, diethoxy dimethyl silane, and diethyl dimethoxy silane. Among them, dimethyldimethoxysilane is preferable.

Examples of monofunctional silane monomers capable of incorporating structure (d) 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.

The primary particles of the fine particles of the present invention have a number average particle diameter of 0.05 μm or more and 0.20 μm or less. When the number average particle diameter of the primary particles falls within the above range, the toner particles can be uniformly covered with the fine particles. Further, stress on the toner can be suppressed, and thus the effect of charging stability can be easily obtained. In the case where the number average particle diameter of the primary particles of the fine particles is less than 0.05 μm, when images each having a low print density are output in large amounts for a long time under a severe environment such as a high temperature and high humidity environment, stress to the toner is increased, and thus there is a risk that the external additive particles are easily embedded in the surface of the toner.

Further, when the number average particle diameter of the primary particles of the fine particles exceeds 0.20 μm, there is a risk that the fine particles are liable to be detached from the surface of the toner. The number average particle diameter of the primary particles of the fine particles can be increased by decreasing the reaction temperature, shortening the reaction time, and increasing the amount of the catalyst in each of the hydrolysis process and the polycondensation process. Further, the number average particle diameter of the primary particles of the fine particles can be reduced by increasing the reaction temperature, extending the reaction time, and reducing the amount of catalyst in each of the hydrolysis process and the polycondensation process.

From the above viewpoints, the number average particle diameter of the primary particles of the fine particles is preferably 0.07 μm or more and 0.18 μm or less, and more preferably 0.08 μm or more and 0.15 μm or less.

In measurement by X-ray fluorescence (XRF), the fine particles contain silicon atoms in a proportion of 20% or more with respect to all elements. When the proportion of silicon atoms with respect to all elements falls within the above range, transferability and durability stability are improved. When the ratio is less than 20%, the charging amount of the fine particles becomes too low, and thus the effect of transferability cannot be easily obtained. The proportion of silicon atoms relative to all elements can be increased by increasing the mixing ratio of the silane monomers capable of being incorporated into structures (a) to (d). The proportion of silicon atoms relative to all elements can be reduced by reducing the mixing ratio of the silane monomers capable of being incorporated into structures (a) to (d). From the viewpoint of chargeability, the upper limit of the proportion of silicon atoms to all elements is preferably 50% or less.

In the fine particles of the present invention, it is preferable that X and Y satisfy the relationship of 0.20.ltoreq.Y/(X+Y) at the point of time when a test piece made of PET is cut to a depth of 50nm by irradiation with Ar-K.alpha.radiation. When Y/(x+y) falls within the above range, the fine particles have moderate elasticity, and thus the durability stability is further improved. The value of Y/(x+y) can be controlled by the mixing ratio of the silane monomers having the structures (a) to (d). For example, Y/(x+y) may be increased by increasing the mixing ratio of the silane monomers capable of introducing the structures (b) to (d) or decreasing the mixing ratio of the silane monomers capable of introducing the structure (a). Further, Y/(x+y) may be reduced by decreasing the mixing ratio of the silane monomers capable of introducing the structures (b) to (d) or increasing the mixing ratio of the silane monomers capable of introducing the structure (a). Y/(X+Y) satisfies the relationship of preferably 0.20.ltoreq.Y/(X+Y). Ltoreq.0.40, more preferably 0.20.ltoreq.Y/(X+Y). Ltoreq.0.30.

In the fine particles of the present invention, it is preferable that X and Y satisfy the relationship of 1.2.ltoreq.X/Y.ltoreq.2.0 at the point in time when a test piece made of PET is cut to a depth of 50nm by irradiation with Ar-K.alpha.rays. When X/Y falls within the above range, the fine particles have moderate elasticity, and thus durability stability is further improved. The value of X/Y can be controlled by the mixing ratio of the silane monomers capable of being incorporated into structures (a) to (d). For example, X/Y may be increased by decreasing the mixing ratio of the silane monomers capable of introducing structures (b) to (d) or increasing the mixing ratio of the silane monomer having structure (a). In addition, the X/Y can be reduced by increasing the mixing ratio of the silane monomers capable of introducing the structures (b) to (d) or decreasing the mixing ratio of the silane monomers capable of introducing the structure (a). Further, X/Y more preferably satisfies the relationship of 1.2.ltoreq.X/Y.ltoreq.1.8.

The Young's modulus of the fine particles of the present invention is preferably 10GPa to 30 GPa. In the case where the young's modulus falls within the above range, when the toner is subjected to stress from a member such as a carrier, the stress is relaxed, and embedding of fine particles to the surface of the toner particles can be further suppressed.

In the case where the young's modulus is 10GPa or more, when the toner is subjected to stress from a member such as a carrier, the fine particles themselves are less likely to break. Further, in the case where the young's modulus is 30GPa or less, when the toner is subjected to stress from a member such as a carrier, the stress is easily relaxed, and embedding of fine particles into the surface of the toner particles can be further suppressed. Therefore, the toner surface state is less likely to change, and charging change of the toner can be further suppressed.

The young's modulus of the fine particles can be controlled by changing the mixing ratio of the above-mentioned monomers and the temperature, time, pH and kind of catalyst of each of the hydrolysis process and the polycondensation process. For example, the young's modulus can be increased by increasing the mixing ratio of the silane monomer capable of being introduced into the structure (a), decreasing the mixing ratio of the silane monomer capable of being introduced into the structures (b) to (d), increasing the temperature of each of the hydrolysis process and the polycondensation process, extending the time of each of the hydrolysis process and the polycondensation process, or increasing the pH of each of the hydrolysis process and the polycondensation process, or the like. The young's modulus can be reduced by decreasing the mixing ratio of the silane monomer capable of being introduced into the structure (a), increasing the mixing ratio of the silane monomer capable of being introduced into the structures (b) to (d), decreasing the temperature of each of the hydrolysis process and the polycondensation process, decreasing the time of each of the hydrolysis process and the polycondensation process, or decreasing the pH of each of the hydrolysis process and the polycondensation process, or the like. The Young's modulus of the fine particles is more preferably 13GPa to 20 GPa.

The surface of the fine particles of the present invention is preferably subjected to a surface treatment with a hydrophobizing agent. That is, the fine particles are preferably particles of a silicon polymer surface-treated with a hydrophobizing agent. The hydrophobizing agent is not particularly limited, but is preferably an organosilicon compound.

Examples thereof may include: alkylsilazane compounds such as hexamethyldisilazane; alkylalkoxysilane compounds such as diethyldiethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, and butyltrimethoxysilane; fluoroalkyl silane compounds such as trifluoropropyl trimethoxysilane; chlorosilane compounds such as dimethyldichlorosilane and trimethylchlorosilane; siloxane compounds such as octamethyl cyclotetrasiloxane; silicone oil; and a silicone varnish.

By the hydrophobization treatment of the fine particle surface, the change in the charge amount of the toner under the high-temperature and high-humidity environment can be further suppressed. In particular, it is preferable to surface-treat the fine particles with at least one compound selected from the group consisting of: alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, siloxane compounds and silicone oils. Further, from the viewpoint of charging stability under a high-temperature and high-humidity environment, it is more preferable to surface-treat the fine particles with an alkylsilazane compound.

From the viewpoint of charge stability under high-temperature and high-humidity environments, the degree of hydrophobicity of the fine particles obtained by the methanol titration method is preferably 50% or more and 60% or less. The degree of hydrophobization is more preferably 53% or more and 58% or less.

Preferably in the presence of fine particles according to the invention ²⁹ In the graph obtained by the Si-NMR measurement, when the total peak area of angelica belonging to the silicon polymer is represented by SA, the peak area ascribed to the following structure (a) is represented by S4, the peak area ascribed to the following structure (b) is represented by S3, and the peak area ascribed to the following structure (c) is represented by S2, SA, S2, S3, and S4 satisfy the following expressions (I) to (III).

0.30≤S4/SA≤0.80···(I)

0≤S3/SA≤0.50···(II)

0.20≤S2/SA≤0.70···(III)

Wherein R is ₁ And R is ₂ Each independently represents a hydrocarbon group having 1 to 6 carbon atoms.

Within the above range, when the toner is subjected to stress from a member such as a carrier, fine particles can be suppressed from being embedded into the toner particle surface and breakage of the fine particles themselves. Further, from the viewpoints of transferability, charging stability and durability stability of the toner, it is more preferable that the relationship of 0.40.ltoreq.S 4/SA.ltoreq.0.70, 0.ltoreq.S 3/SA.ltoreq.0.10 and 0.30.ltoreq.S 2/SA.ltoreq.0.60 is satisfied because of Si-CH in the fine particles ₃ The amount of existence of (c) is optimal.

When the fine particles of the present invention are used as an external additive for toner, the content of the fine particles in the toner base particles is preferably 0.1 parts by mass or more and 20.0 parts by mass or less relative to 100 parts by mass of the toner base particles from the viewpoint of charging stability. Further, the content is more preferably 0.5 parts by mass or more and 15.0 parts by mass or less, and still more preferably 1.0 parts by mass or more and 10.0 parts by mass or less.

In the case where the content of the external additive for toner is less than 0.1 parts by mass, when images each having a low print density are output in large amounts for a long period of time under a severe environment such as a high-temperature and high-humidity environment, stress on toner cannot be suppressed, and an improvement effect on durability stability and charging stability cannot be easily obtained.

Further, in the case where the content of the fine particles exceeds 20.0 parts by mass, when images each having a high print density are output for a long period of time, there is a risk that filming of the external additive particles on the carrier or the photosensitive member may occur.

[ toner particles ]

Next, the constitution of the toner particles externally added with the above fine particles of the present invention is described in detail.

< binder resin >

The binder resin used in the toner of the present invention is not particularly limited, and the following polymer or resin may be used.

For example, it is possible to use: homopolymers of styrene and its substitution products, such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene; styrenic copolymers such as styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-alpha-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl ether copolymer, styrene-vinylethyl ether copolymer, styrene-vinylmethyl ketone copolymer, and styrene-acrylonitrile-indene copolymer; polyvinyl chloride; a phenolic resin; a natural modified phenolic resin; a natural resin modified maleic acid resin; an acrylic resin; methacrylic resins; polyvinyl acetate; a silicone resin; a polyester resin; polyurethane; a polyamide resin; furan resin; an epoxy resin; a xylene resin; polyvinyl butyral; a terpene resin; coumarone-indene resin; and petroleum-based resins. Among them, polyester resins are preferable from the viewpoints of endurance stability and charging stability.

Further, from the viewpoints of environmental stability and charging stability, the acid value of the polyester resin is preferably 0.5mgKOH/g or more and 40mgKOH/g or less. Acid value in polyester resin and Si-CH in fine particles ₃ Interact with each other. Therefore, durability and toner chargeability under high-temperature and high-humidity environments can be further improved. The acid value is more preferably 1 to 20mgKOH/g, still more preferably 1 to 15 mgKOH/g.

< colorant >

A colorant may be used in the toner of the present invention as needed. Examples of the colorant include the following.

As the black colorant, for example, carbon black, and a colorant toned to black with a yellow colorant, a magenta colorant, and a cyan colorant are given. Although pigments alone may be used as the colorant, it is preferable to use a dye and a pigment in combination to improve the definition of the colorant in terms of the quality of a full-color image.

As the pigment for magenta toner, for example, c.i. pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, or 282; c.i. pigment violet 19; and c.i. vat red 1, 2, 10, 13, 15, 23, 29, or 35.

As the dye for magenta toner, for example, an oil-soluble dye such as c.i. solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, or 121; c.i. disperse red 9; c.i. solvent violet 8, 13, 14, 21 or 27; c.i. disperse violet 1; and basic dyes such as c.i. basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, or 40; and c.i. basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27 or 28.

As the pigment for cyan toner, for example, c.i. pigment blue 2, 3, 15:2, 15:3, 15:4, 16, or 17; c.i. vat blue 6; c.i. acid blue 45; and copper phthalocyanine pigments in which the phthalocyanine skeleton is substituted with 1 to 5 phthalimidomethyl groups.

As a dye for cyan toner, for example, c.i. solvent blue 70 is given.

As the pigment for yellow toner, for example, c.i. pigment yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, or 185; and c.i. vat yellow 1, 3 or 20.

As a dye for yellow toner, for example, c.i. solvent yellow 162 is given.

The content of the colorant is preferably 0.1 part by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

< wax >

Waxes may be used in the toner of the present invention as needed. Examples of waxes include the following.

Hydrocarbon-based waxes such as microcrystalline wax, paraffin wax, and fischer-tropsch wax; for example, an oxide of a hydrocarbon wax such as an oxidized polyethylene wax, or a block copolymer thereof; waxes each containing a fatty acid ester as a main component, such as carnauba wax; and waxes obtained by partially or completely deacidifying fatty acid esters, such as deacidified carnauba wax.

Further, examples include the following: saturated straight chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brasilenic acid, eleostearic acid and stearidonic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauba alcohol, cetyl alcohol, and melissa alcohol; polyols, 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 alcohol, behenyl alcohol, carnauba alcohol, cetyl alcohol and melissa alcohol; fatty acid amides such as oleamide, oleamide and lauramide; saturated fatty acid bisamides such as methylene bis stearamide, ethylene bis decanoamide, ethylene bis lauramide, and hexamethylene bis stearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N '-dioleyladipamide, and N, N' -dioleylsebacamide; aromatic bisamides such as m-xylene bisstearamide and N, N' -distearyl isophthalamide; fatty acid metal salts (commonly referred to as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes each obtained by grafting a vinyl monomer such as styrene or acrylic acid to an aliphatic hydrocarbon wax; partial esters of fatty acids with polyols, for example, monoglycerides of behenic acid; and methyl ester compounds each having a hydroxyl group obtained by hydrogenation of vegetable oils and fats.

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.

< Charge control agent >

The charge control agent may be incorporated into the toner of the present invention as needed. Although a known charge control agent can be utilized as the charge control agent to be incorporated into the toner, a metal compound of an aromatic carboxylic acid is particularly preferable because the compound is colorless, increases the charging speed of the toner, and can stably maintain a constant charge amount.

Examples of the negative charge control agent include a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, a polymer compound having a sulfonic acid or carboxylic acid in a side chain, a polymer compound having a sulfonate or sulfonate in a side chain, a polymer compound having a carboxylate or carboxylate in a side chain, a boron compound, a urea compound, a silicon compound, and calixarene. The charge control agent may be added internally to the toner particles, or may be added externally thereto.

The amount of the charge control agent to be added is preferably 0.2 parts by mass or more and 10.0 parts by mass or less relative to 100 parts by mass of the binder resin.

< inorganic Fine powder >

In the toner of the present invention, other inorganic fine powders may be used in combination as required in addition to the above-described fine particles. The inorganic fine powder may be internally added to the toner particles or may be mixed with the toner base particles as an external additive. As the external additive, an inorganic fine powder such as silica is preferably used. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As the external additive for improving fluidity, a specific surface area of 50m is preferable ² Above/g and 400m ² Inorganic fine powder of not more than/g. Inorganic fine particles having a specific surface area within the above-described range may be used in combination, thereby achieving both improvement of fluidity and stabilization of durability. 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 relative to 100 parts by mass of the toner particles. When the above range is satisfied, the effect of charging stability is easily obtained.

< developer >

The toner of the present invention, which can be used as a one-component-system developer, is preferably used as a two-component-system developer by mixing with a magnetic carrier to further improve dot reproducibility thereof, because a stable image can be obtained for a long period of time. That is, a two-component-type developer containing a toner and a magnetic carrier is preferable, wherein the toner is the toner of the present invention.

Examples of magnetic carriers that can be used include commonly known magnetic carriers including: surface oxidized iron powder or non-oxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth; alloy particles thereof; oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) each containing a magnetic material and a binder resin that holds the magnetic material in a state in which the magnetic material is dispersed.

When a toner is mixed with a magnetic carrier to be used as a two-component-system developer, satisfactory results are generally obtained by setting the carrier mixing ratio at this time (as the toner concentration in the two-component-system developer) to preferably 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less.

< method for producing toner particles and method for producing toner >

The method of producing the toner particles is not particularly limited, and conventionally known production methods such as suspension polymerization method, emulsion aggregation method, melt-kneading method, or dissolution suspension method may be employed.

The toner may be obtained by mixing the resulting toner particles with inorganic fine particles and any other external additives as needed. The mixing of the toner particles with the inorganic fine particles and other external additives can be performed using a mixing apparatus such as a twin cone mixer, a V-type mixer, a tumbler mixer, a super mixer, a henschel mixer, a nod mixer, and MECHANO HYBRID (manufactured by Nippon cofe & Engineering co., ltd.) or NOBILTA (manufactured by Hosokawa Micron Corporation).

In order to control the fixation rate of the fine particles to the toner particles based on the water washing method, it is preferable to mix the fine particles with the toner particles to obtain a toner particle mixture, and then heat-treat. That is, the method of producing toner preferably includes: a mixing process of mixing toner particles with fine particles to provide a toner particle mixture; and a heat treatment step of heat-treating the toner particle mixture. The fixation rate of fine particles can be improved by performing a heat treatment process. The fixation ratio of the fine particles to the toner particles (fixation ratio of the fine particles by the water washing method) is preferably 50% or more. In the case where the fixation ratio of the fine particles falls within the above range, the durability stability and the charging stability are further improved even when an image is output in large amounts for a long time, because the fine particles are not easily detached from the toner. Further, even when printing is performed for a long period of time in an environment where toner is excessively charged, such as a low humidity environment, fine particles are not easily detached from the toner, and thus excessive charging of the toner is suppressed, with the result that an effect of improving transferability is further obtained. The fixation ratio is more preferably 70% or more. The upper limit of the fixation ratio is not particularly limited, but it is preferably 99% or less, more preferably 95% or less. The fixation ratio of the fine particles to the toner particles can be controlled by the temperature of hot air in the heat treatment process.

For example, the heat treatment may be performed with hot air by using the heat treatment apparatus shown in fig. 1.

The heat treatment apparatus includes: a process chamber 6 for heat-treating the toner particle mixture, a toner particle mixture supply unit for supplying the toner particle mixture to the process chamber 6, a hot air supply unit 7 for supplying hot air for heat-treating the toner particle mixture supplied from the toner particle mixture supply unit, and a recovery unit 10 for discharging the heat-treated toner particles from a discharge port formed in the process chamber 6 to the outside of the process chamber 6 and recovering the heat-treated toner particles.

The heat treatment apparatus shown in fig. 1 further includes an adjusting unit 9 as a cylindrical member, and the treatment chamber 6 has a cylindrical shape covering the outer peripheral surface of the adjusting unit 9. A hot air supply unit 7 is provided at one end side of the cylindrical treatment chamber 6 so that hot air flows while rotating in the treatment chamber 6 having a cylindrical shape. Further, the toner particle mixture supply unit includes a plurality of supply pipes 5 provided on the outer periphery of the process chamber 6.

Further, the discharge port provided in the process chamber 6 is provided on the outer periphery of the end of the process chamber 6 on the opposite side to the side where the hot air supply unit 7 is provided, so as to exist on an extension line along the rotation direction of the toner particle mixture. The heat treatment using the heat treatment apparatus having the above-described constitution is described below.

The toner particle mixture quantitatively fed by the raw material quantitative feeding unit 1 is introduced into an introduction pipe 3 provided on the vertical line of the raw material quantitative feeding unit 1 by the compressed gas regulated by the compressed gas flow rate regulating unit 2. The mixture passing through the introduction pipe is uniformly dispersed by a conical projection member 4 provided at the center of the introduction pipe 3, introduced into a supply pipe 5 extending radially in 8 directions, and introduced into a treatment chamber 6 in which heat treatment is performed.

At this time, the flow of the mixture supplied to the process chamber 6 is regulated by a regulating unit 9 for regulating the flow of the mixture, which is provided in the process chamber 6. Thus, the mixture supplied to the process chamber 6 is heat-treated while swirling in the process chamber 6, and then cooled.

Heat for heat-treating the supplied mixture is supplied from the hot air supply unit 7 and distributed by means of the distribution member 12, and hot air is introduced into the treatment chamber 6 while being swirled in a spiral shape by means of the swirling member 13 for swirling the hot air. With such a configuration, the swirling member 13 for swirling the hot air has a plurality of blades, and the swirling of the hot air can be controlled according to the number and angle of the blades. Hot air is supplied from the hot air supply unit outlet 11.

The heat-treated toner particles are cooled by the cold air supplied from the cold air supply unit 8 (cold air supply units 8-1, 8-2, and 8-3).

Next, the cooled toner particles are recovered by the recovery unit 10 existing at the lower end of the process chamber. The recovery unit has a constitution provided with a blower (not shown) at the front end thereof, and sucks and conveys the particles by means of the blower.

Further, 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 may be the same direction, and the recovery unit 10 of the thermal spheroidizing apparatus is provided at the outer peripheral portion of the processing chamber, thereby maintaining the swirling direction of the powder particles caused to swirl. The cool air supplied from the cool air supply unit 8 is supplied from the outer peripheral portion of the apparatus to the inner peripheral surface of the processing chamber in the horizontal direction and the tangential direction.

After the heat-treated toner particles are obtained, the heat-treated toner particles may be mixed with various external additives. As the mixing apparatus, a mixing apparatus such as a twin cone mixer, a V-type mixer, a tumbler mixer, a super mixer, a henschel mixer, a noda mixer, a MECHANO HYBRID (manufactured by Nippon cofe & Engineering co., ltd.) or NOBILTA (manufactured by Hosokawa Micron Corporation) may be used.

[ method of measuring various physical Properties ]

The method of measuring various physical properties is described below.

< separation of fine particles and toner particles from toner >

Each physical property can be measured by using fine particles separated from the toner by the following method. To 100mL of ion-exchanged water, 200g of sucrose (manufactured by Kishida Chemical co., ltd.) was added and the sucrose was dissolved in the ion-exchanged water with heating with hot water to prepare a sucrose thick liquid. 31g of a sucrose concentrate and 6ml of a surfactant-containing N (10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument, which is formed of a nonionic surfactant, an anionic surfactant and an organic builder and has a pH of 7, manufactured by Fujifilm Wako Pure Chemical Corporation) were put into a tube for centrifugal separation to prepare a dispersion. 1g of toner was added to the dispersion liquid and the toner lump was loosened with a spatula or the like.

The tube for centrifugal separation was shaken in the above-mentioned shaking table under conditions of 350 reciprocations per minute for 20 minutes. After shaking, the solution was transferred to a glass tube for horizontal rotor (50 mL) and centrifuged in a centrifuge at 3,500rpm for 30 minutes. In the glass tube after centrifugal separation, toner exists in the uppermost layer, and fine particles exist on the aqueous solution side of the lower layer. The aqueous solution of the lower layer was collected and centrifuged to separate into sucrose and fine particles, to thereby collect the fine particles. Centrifugal separation is repeated as necessary to sufficiently perform separation, and then the dispersion is dried and fine particles are collected.

When a plurality of fine particles are added, the fine particles of the present invention can be sorted by using a centrifugal separation method or the like.

< method for measuring number average particle diameter of primary particles of Fine particles >

The number average particle diameter of the primary particles of the fine particles can be determined by measurement using a centrifugal sedimentation method. Specifically, 0.01g of the dried external additive particles were put into a 25mL glass vial, and 0.2g of 5% triton solution and 19.8gRO water were added to the vial to thereby prepare a solution. Next, a probe of an ultrasonic dispersion machine (tip inside the tip) was immersed in the solution, and ultrasonic dispersion was performed at an output of 20W for 15 minutes to thereby provide a dispersion liquid. Subsequently, the number average particle diameter of the primary particles was measured by using a centrifugal sedimentation particle size distribution measuring device DC24000 of CPS Instruments, inc. The rotational speed of the disk was set at 18,000rpm, and the true density was set at 1.3g/cm ³ . The device was calibrated prior to measurement by using polyvinyl chloride particles with an average particle size of 0.476 μm.

< method for measuring acid value of Binder resin >

The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid components such as free fatty acids and resin acids contained in 1g of the sample. The acid value was measured in accordance with JIS-K0070-1992 as described below.

(1) Reagent(s)

The phenolphthalein solution was provided by dissolving 1.0g of phenolphthalein in 90mL of ethanol (95 vol%) and adding ion-exchanged water to fix the volume to 100 mL.

7g of extra potassium hydroxide was dissolved in 5mL of water, and ethanol (95 vol%) was added to fix the volume to 1L. The resultant was placed in an alkali-resistant container so as not to be contacted with carbonic acid gas or the like, and allowed to stand in the alkali-resistant container for 3 days, and then filtered to provide a potassium hydroxide solution. The resulting potassium hydroxide solution was stored in an alkali-resistant container. When 25mL of 0.1mol/L hydrochloric acid was placed in an conical flask and several drops of phenolphthalein solution were added and then the solution was dropped with potassium hydroxide solution, the coefficient of the potassium hydroxide solution was determined by the amount of potassium hydroxide solution required for neutralization. The 0.1mol/L hydrochloric acid to be used was produced in accordance with JIS K8001-1998.

(2) Operation of

(A) Main test

2.0g of the crushed sample was precisely weighed in a 200mL Erlenmeyer flask, and 100mL of a toluene/ethanol (2:1) mixed solution was added to dissolve the sample over 5 hours. Then, a few drops of phenolphthalein solution was added as an indicator, and titration was performed with potassium hydroxide solution. The endpoint of the titration is defined as the point at which the light pink color of the indicator lasts about 30 seconds.

(B) Blank test

Titration was performed in the same manner as in the above-described operation, except that no sample was used (i.e., only toluene/ethanol (2:1) mixed solution was used).

(3) The acid value was calculated by substituting the obtained result into the following equation:

A＝[(C-B)×f×5.61]/S

wherein A represents an acid value (mgKOH/g), B represents an addition amount (mL) of a potassium hydroxide solution in a blank test, C represents an addition amount (mL) of a potassium hydroxide solution in a main test, "f" represents a coefficient of a potassium hydroxide solution, and S represents a mass (g) of a sample.

< measurement of acid value of polyester resin from toner >

As a method for measuring the acid value of the polyester resin from the toner, the following method can be used. The polyester resin was separated from the toner and the acid value was measured by the following method.

The toner is dissolved in Tetrahydrofuran (THF), and the solvent is distilled off from the resulting soluble matter under reduced pressure to thereby provide a Tetrahydrofuran (THF) soluble fraction of the toner.

The Tetrahydrofuran (THF) soluble component of the resulting toner was dissolved in chloroform to prepare a sample solution having a concentration of 25 mg/mL.

3.5mL of the obtained sample solution was injected into the following apparatus, and the component having a molecular weight of 2,000 or more was fractionated as a resin component under the following conditions.

Preparation type GPC device: preparative HPLC LC-980 type manufactured by Japan Analytical industrial co., ltd

Preparation of the column: JAIGEL 3H, JAIGEL H (manufactured by Japan Analytical Industry co., ltd.)

Eluent: chloroform (chloroform)

Flow rate: 3.5mL/min

After fractionation of the high molecular weight component derived from the resin, the solvent is distilled off under reduced pressure. The resultant was further dried under reduced pressure at 90℃for 24 hours. The above operation was repeated until about 2.0g of the resin component was obtained. By using the obtained sample, the acid value was measured according to the procedure described above.

< method of measuring weight average particle diameter (D4) of toner particles >

The weight average particle diameter (D4) of the toner particles was calculated by measuring and analyzing the measurement data with the number of effective measurement channels of 25,000 by using a precision particle size distribution measuring apparatus "Coulter Counter Multisizer 3" (trademark, manufactured by Beckman Coulter, inc.) based on the pore resistance method equipped with a 100 μm mouth tube and its accompanying dedicated software "Beckman Coulter Multisizer version 3.51" (manufactured by Beckman Coulter, inc.) for setting the measurement conditions and analyzing the measurement data.

An aqueous electrolyte solution such as "ISOTON II" (manufactured by Beckman Coulter, inc.) prepared by dissolving extra sodium chloride in ion-exchanged water so as to have a concentration of about 1 mass% can be used for measurement.

Prior to measurement and analysis, specialized software was set up as described below.

In the "change standard measurement method (SOM)" interface of the dedicated software, the total count of the control mode was set to 50,000 particles, the number of measurements was set to 1, and the value obtained by using "standard particles having particle diameters of 10.0 μm each" (manufactured by Beckman Coulter, inc.) was set to Kd value. The threshold and noise level are automatically set by pressing a threshold/noise level measurement button. Further, the current was set to 1,600 μa, the gain was set to 2, and the electrolyte solution was set to ISOTON II, and a check mark was set in a check box as to whether or not the oral tube was rinsed after measurement.

In the interface of "pulse-to-particle diameter conversion setting" of the dedicated software, the element interval is set to logarithmic particle diameter, the number of particle diameter elements is set to 256, and the particle diameter range is set to a range of 2 μm to 60 μm.

The specific measurement method is as follows.

(1) About 200mL of the aqueous electrolyte solution was added to a glass 250mL round bottom beaker specific for Multisizer 3. The beaker was placed in a sample stand, and the aqueous electrolyte solution in the beaker was stirred with a stirring rod at 24 rpm in a counterclockwise direction. Dirt and air bubbles within the mouth tube are then removed by the "mouth tube flushing" function of the dedicated software.

(2) About 30mL of the aqueous electrolyte solution was added to a glass 100mL flat bottom beaker. About 0.3mL of a diluted solution prepared by diluting "conteminon N" (a 10 mass% aqueous solution of a neutral detergent for cleaning a precision measuring instrument, which is formed of a nonionic surfactant, an anionic surfactant and an organic builder and has a pH of 7, manufactured by Fujifilm Wako Pure Chemical Corporation) 3 times by mass with ion-exchanged water was added to the aqueous electrolyte solution as a dispersant.

(3) A predetermined amount of ion exchange water was added to a water tank of an ultrasonic dispersion unit "ultrasonic dispersion system Tetora 150" (manufactured by Nikkaki Bios co., ltd.) in which two oscillators each having an oscillation frequency of 50kHz are built in so as to shift the phase by 180 °, and the power output is 120W. About 2mL of Contaminon N was added to the water tank.

(4) The beaker in the above (2) was set in the beaker fixing hole of the ultrasonic dispersion unit, and the ultrasonic dispersion unit was started. Then, the height position of the beaker was adjusted to maximize the resonance state of the liquid surface of the electrolyte aqueous solution in the beaker.

(5) In a state where the aqueous electrolyte solution was irradiated with ultrasonic waves, about 10mg of toner was gradually added and dispersed in the aqueous electrolyte solution in the beaker in the above (4). Then, the ultrasonic dispersion treatment was continued for another 60 seconds. In ultrasonic dispersion, the temperature of water in a water tank is appropriately adjusted to 10 ℃ or higher and 40 ℃ or lower.

(6) The aqueous electrolyte solution of the above (5) having the toner dispersed therein was added dropwise to the round-bottomed beaker of the above (1) provided in the sample stage with a pipette, and the concentration of the toner to be measured was adjusted to about 5%. Then, measurement was performed until 50,000 particles were measured.

(7) The measurement data are analyzed by special software attached to the apparatus, and the weight average particle diameter is calculated (D4). When the dedicated software is set to display "graph/volume%", the "average diameter" on the "analysis/volume statistics (arithmetic average)" interface of the dedicated software is the weight average particle diameter (D4).

< method of measuring Young's modulus of fine particles >

Young's modulus of the fine particles was determined by a micro compression test using Hysicron PI 85L PicoInmenter (manufactured by Bruker Corporation).

Young's modulus (MPa) was calculated from the slope of the curve (load displacement curve) of displacement (nm) and test force (μN) obtained by the measurement.

Device and clamp

Base system: hysicron PI 85L

Measuring pressure head: circular flat head press with diameter of 1 mu m

SEM used: thermo Fisher Versa 3D

SEM conditions: -10℃tilt, 13pA at 10keV

Measurement condition

Measurement mode: displacement control

Maximum displacement: 30nm of

Displacement speed: 1nm/sec

Holding time: 2sec

Unloading speed: 5nm/sec

Analysis method

In the resulting load displacement curve, a hertz analysis was applied to the curve obtained when compressing 0nm to 10nm to thereby calculate the young's modulus of the fine particles.

Sample preparation

Fine particles attached to silicon wafer

< method for measuring fixation Rate of Fine particles >

Methods for measuring the fixation rate of fine particles are described. First, fine particles contained in the toner before the water washing treatment are quantified. The Si element intensity in the toner was measured by using a wavelength-dispersive X-ray fluorescence analyzer "Axios advanced" (manufactured by PANalytical Corporation). Then, in the same manner, the Si element strength in the toner after the following water washing treatment was measured. The fixation (%) can be calculated by the following equation.

Fixation ratio (%) = (Si element strength in toner after water washing treatment/Si element strength in toner before water washing treatment) ×100

The conditions of the water washing treatment are described below.

(washing treatment step)

20.7g of sucrose (manufactured by Kishida Chemical co., ltd.) was dissolved in 10.3g of an aqueous sucrose solution in ion-exchanged water and 6mL of Contaminon N (a neutral detergent for precision measuring instrument cleaning formed of a nonionic surfactant, an anionic surfactant and an organic builder and having a pH of 7) serving as a surfactant were placed in a 30mL glass vial and thoroughly mixed to thereby prepare a dispersion. Further, as the Glass vial, for example, VCV-30 manufactured by Nichiden-Rika Glass Co., ltd. Having an outer diameter of 35mm and a height of 70mm can be used. To the dispersion, 1.0g of toner was added and allowed to stand until the toner settled, to thereby prepare a pre-treatment dispersion. The pre-treatment dispersion was shaken with a shaking table (model YS-8D: manufactured by Yayoi co., ltd.) at a shaking speed of 200rpm for 5 minutes to thereby detach the fine particles from the surfaces of the toner particles. By this operation, the fine particles weakly attached to the surfaces of the toner particles are detached from the surfaces of the toner particles, but the fine particles firmly attached to the surfaces of the toner particles remain on the surfaces of the toner particles. Separation between toner particles with a part of fine particles remaining on the surface and the separated fine particles is performed with a centrifuge. The centrifugation operation was performed by using a small-sized bench-top centrifuge "H-19F" (manufactured by Kokusan Co., ltd.) at 3,700rpm for 30 minutes. After centrifugal separation, the toner having fine particles remaining thereon is collected by suction filtration, and dried to provide a water-washed toner.

In solid form ²⁹ In Si-NMR, peaks are detected in different displacement regions depending on the structure of the functional group bound to Si in the constituent compound of the fine particles. The structure bound to Si can be determined by determining the position of each peak by using a standard sample. The ratio of the amounts of the constituent compounds present can be calculated from the peak areas obtained. The ratio of the peak areas of the M cell structure, the D cell structure, the T cell structure, and the Q cell structure to the total peak area can be found by calculation.

For solids ²⁹ The measurement conditions of Si-NMR are specifically as follows.

The device comprises: JNM-ECX5002 (JEOL RESONANCE)

Temperature: room temperature

The measuring method comprises the following steps: DDMAS 29Si 45 DEG

Sample tube: zirconia (zirconia)

Sample: filling into test tubes in powder state

Sample rotation speed: 10kHz

Relaxation delay: 180s

Number of scans: 2,000 times

After the measurement, the various silane components having different substituents and linking groups in the sample were peak-separated by curve fitting to the following M-unit structure, D-unit structure, T-unit structure, and Q-unit structure, and the respective peak areas were calculated.

Curve fitting was performed by using software EXcalibur for Windows (trade mark) version 4.2 (EX series) for JNM-EX 400 manufactured by JEOL ltd. "1D Pro" is clicked from the menu icon to read the measurement data. Next, a "curve fitting function" is selected from "commands" in the menu bar, and curve fitting is performed. Curve fitting is performed for each component so as to minimize the difference between the synthesized peak obtained by synthesizing each peak obtained by curve fitting and the peak of the measurement result (synthesized peak difference).

M unit structure: (Ra) (Rb) (Rc) Si-O- (S1')

D unit structure: (Rd) (Re) Si (-O-) ₂ (S2′)

T unit structure: rfSi (-O-) ₃ (S3′)

Q unit structure: si (-O-) ₄ (S4′)

The total peak area corresponding to the aforementioned peaks of the silicon polymer is represented by SA. That is, let (S1 '+s2' +s3 '+s4')=sa.

Ra, rb, rc, rd, re and Rf in the formulae (S1 '), (S2 ') and (S3 ') each represent a hydrocarbon group having 1 to 6 carbon atoms bonded to silicon. The hydrocarbyl group is preferably an alkyl group.

From the obtained peak areas, a peak area S3 corresponding to the structure (a), a peak area S4 corresponding to the structure (b), and a peak area S2 corresponding to the structure (c) were calculated. When the structure needs to be confirmed in more detail, the method can ¹³ C-NMR ¹ Measurement results of H-NMR and ²⁹ the Si-NMR measurements were identified together. From the thus obtained SA, S2, S3 and S4, S3/SA, S4/SA and S2/SA are calculated.

< method for measuring the degree of hydrophobization of Fine particles >

The degree of hydrophobicity of the fine particles of the present invention was calculated by methanol titration. Specifically, the degree of hydrophobization was measured by the following procedure. In a mixed liquid obtained by adding 0.5g of external additive particles for toner to 50mL of RO water, methanol was added dropwise from a burette while stirring the mixed liquid until the entire amount of external additive particles for toner was wetted. Whether the entire amount has been wetted is judged by whether all fine particles floating on the water surface have been submerged and suspended in the liquid. In this case, the percentage value of methanol added dropwise at the end of the addition with respect to the total amount of the mixed liquid and methanol is defined as the degree of hydrophobization. Higher values of the degree of hydrophobization indicate higher hydrophobicity. The degree of hydrophobization of the fine particles of the present invention is preferably 50% or more and 60% or less from the viewpoint of charge stability. Further, the degree of hydrophobization is more preferably 53% or more and 58% or less.

< method of measuring Fine particle surface treatment agent >

The fine particle surface treatment agent was analyzed by pyrolysis GC-MS (gas chromatography mass spectrometry).

The measurement conditions are specifically described below.

The device comprises: GC6890A (manufactured by Agilent Technologies Corporation), pyrolyzer (manufactured by Japan Analytical Industry co., ltd.)

Column: HP-5ms 30m

Pyrolysis temperature: 590 DEG C

The fine-particle surface treatment agent was identified by identifying each peak position in a graph obtained by measurement using a standard sample.

< method of measuring the proportion of silicon atoms in Fine particles by X-ray fluorescence (XRF) >)

The measurement of the proportion of silicon atoms in the fine particles was performed in accordance with JIS K0119-1969 as described below.

As the measuring means, a wavelength-dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical Corporation) and dedicated software "superqver.4.0f" (manufactured by PANalytical Corporation) attached to the means for setting measurement conditions and analyzing measurement data were used. Rh was used as the anode of the X-ray tube. The measurement atmosphere was set to be a vacuum atmosphere. The measurement diameter (collimator shield diameter) was set to 10mm, and the measurement time was set to 10 seconds. Further, when measuring light elements, the elements are detected with a Proportional Counter (PC). When measuring heavy elements, a Scintillation Counter (SC) is used to detect the elements.

As a measurement sample, pellets obtained by placing about 1g of the fine particles in a dedicated aluminum ring for compression, flattening the fine particles, and pressurizing the fine particles at 20MPa for 300 seconds by using a tablet forming compressor "BRE-32" (manufactured by Maekawa Testing Machine mfg.co., ltd.) to thereby shape the fine particles to a thickness of about 2mm and a diameter of about 20mm were used.

The measurement was performed under the above conditions, the element was identified based on the peak position of the obtained X-ray, and the concentration thereof was calculated from the count rate (unit: cps) as the number of X-ray photons per unit time. The formula is as follows.

The ratio of silicon atoms in the fine particles [% ] = (content of silicon atoms in the fine particles [ kcps ])/(content of atoms in the fine particles [ kcps ]) x 100

< method of measuring the proportion of silicon atoms in Fine particles by XPS >

The proportion of the element present in the fine particles was measured by using XPS. The elemental concentration of the silicon element to be measured is represented by dSi, the elemental concentration of the oxygen atom is represented by dO, and the elemental concentration of the carbon atom is represented by dC, and the total amount thereof is assumed to be 100.0 atomic%. The concentration dSi in this case was calculated.

The measurement conditions of XPS are described below.

The device comprises: PHI 5000VERSA Probe II (ULVAC-PHI, inc.)

Radiation: al K alpha ray

And (3) outputting: 25W 15kV

Photoelectron acceptance angle: 45 degree

By energy: 58.7eV

Step size: 0.125eV

XPS peak: c1 s, O1 s, si 2p

GUN type: GCIB

Time: 10min

Interval: 10sec

Sputtering setting: 5kV (kV)

The sample was placed in a sample setting hole of 2mm diameter and 2mm depth machined on an XPS-specific platen.

As a measurement principle, photoelectrons are generated by using an X-ray source, and energy based on a chemical bond inherent to a substance is measured. Monochromatic Al-K alpha is used as X-ray and the measurement is carried out under the above-mentioned conditions.

< method of measuring X and Y of fine particles by XPS >

X and Y in the fine particles were measured by using XPS. The peak of the silicon element to be measured is separated into a peak derived from X and a peak derived from Y to find X and Y.

The measurement conditions are as follows.

The device comprises: PHI 5000VERSA Probe II (ULVAC-PHI, inc.)

Radiation: al K alpha ray

And (3) outputting: 25W 15kV

Photoelectron acceptance angle: 45 degree

By energy: 58.7eV

Step size: 0.125eV

XPS peak: c1 s, O1 s, si 2p

GUN type: GCIB

Time: 10min

Interval: 10sec

Sputtering setting: 5kV (kV)

As a measurement principle, photoelectrons are generated by using an X-ray source, and energy based on a chemical bond inherent to a substance is measured. Monochromatic Al-K alpha is used as X-ray and the measurement is carried out under the above-mentioned conditions. Then, the total peak area of silicon atoms having a bond energy of 102eV to 104eV was divided into a peak area derived from X and a peak area derived from Y to find the area. The peak area with bond energy from 102eV to 103eV is derived from Y, and the peak area with bond energy from 103eV to 104eV is derived from X.

The sputtering rate (ratio of depth to time) was measured in advance with a test piece made of PET. The time required for cutting the PET-made test piece to 2nm, 20nm and 50nm was measured. The depth of cut in the test piece made of PET was observed using a scanning electron microscope. As a test piece made of PET, a test piece having a number average molecular weight (Mn) of 45,000, a thickness of 5mm and a surface roughness (Ra) of 0.01 μm was used.

Examples

The present invention will be described more specifically with reference to the following examples. However, the present invention is by no means limited to these examples. Unless otherwise indicated, "parts" in the following formulations are by mass.

< production example of fine particle 1 >

1. Hydrolysis and polycondensation Process

(1) 43.2. 43.2gRO water, 0.008g acetic acid as catalyst and 19.0g dimethyldimethoxy silane were added to a 500mL beaker and stirred at 45℃for 5 minutes.

(2) 28.8. 28.8gRO water, 380.0g of methanol, 4.0g of 28% ammonia water and 35.4g of tetraethoxysilane were added to the resultant, followed by stirring at 30℃for 3.0 hours to thereby provide a raw material solution.

2. Granulation process

To a 2,000mL beaker was added 1,000g of RO water, and the raw material solution obtained by the above-mentioned "1. Hydrolysis and polycondensation step" was added dropwise to the water at 25℃with stirring over 10 minutes. Thereafter, the mixture was warmed to 60 ℃ and stirred for 1.5 hours while maintaining the temperature at 60 ℃ to thereby provide a dispersion of fine particles each containing silicon.

3. Hydrophobization step

To the dispersion liquid of fine particles each containing silicon obtained by the above "2. Granulation step", 12.0g of hexamethyldisilazane as a hydrophobizing agent was added, and the mixture was stirred at 60 ℃ for 3.0 hours. After the resultant was left to stand for 5 minutes, the powder precipitated in the lower part of the solution was recovered by suction filtration and dried under reduced pressure at 120 ℃ for 24 hours to thereby provide fine particles 1. The number average particle diameter of the primary particles of the fine particles 1 was 0.12. Mu.m. The physical properties of the fine particles 1 are shown in tables 1-1 to 1-2.

< production example of fine particles 2 >

Fine particles 2 were obtained in the same manner as in the production example of fine particles 1 except that the amount of dimethyldimethoxysilane was changed to 10.9g in the above-described (1. Hydrolysis and polycondensation step), and the amount of tetraethoxysilane was changed to 16.3g in (2) and 27.2g of trimethoxymethylsilane was added. The physical properties of the obtained fine particles 2 are shown in tables 1-1 to 1-2.

< production example of fine particles 3 >

Fine particles 3 were obtained in the same manner as in the production example of fine particles 1 except that the amount of dimethyldimethoxysilane was changed to 6.3g in the above-mentioned (1) hydrolysis and polycondensation step "and the amount of tetraethoxysilane was changed to 48.1g in (2). The physical properties of the obtained fine particles 3 are shown in tables 1-1 to 1-2.

< production example of fine particles 4 >

Fine particles 4 were obtained in the same manner as in the production example of fine particles 1 except that the stirring time was changed to 2.0 hours in the above-mentioned (2) of the "hydrolysis and polycondensation step". The physical properties of the obtained fine particles 4 are shown in tables 1-1 to 1-2.

< production example of fine particles 5 >

Fine particles 5 were obtained in the same manner as in the production example of fine particles 1 except that the stirring time was changed to 4.0 hours in the above-mentioned (2) of the "hydrolysis and polycondensation step". The physical properties of the obtained fine particles 5 are shown in tables 1-1 to 1-2.

< production example of fine particles 6 >

Fine particles 6 were obtained in the same manner as in the production example of fine particles 1 except that the stirring time was changed to 1.5 hours in the above-mentioned (2) of the "hydrolysis and polycondensation step". The physical properties of the obtained fine particles 6 are shown in tables 1-1 to 1-2.

< production example of fine particles 7 >

Fine particles 7 were obtained in the same manner as in the production example of fine particles 1 except that the stirring time was changed to 4.5 hours in the above-mentioned (2) of the "hydrolysis and polycondensation step". The physical properties of the obtained fine particles 7 are shown in tables 1-1 to 1-2.

< production example of fine particles 8 >

The fine particles 8 were obtained in the same manner as in the production example of the fine particles 1, except that the hydrophobizing agent to be used in the above-described "3. Hydrophobizing step" was changed to octamethyl cyclotetrasiloxane. The physical properties of the obtained fine particles 8 are shown in tables 1-1 to 1-2.

< production example of fine particles 9 >

The fine particles 9 were obtained in the same manner as in the production example of the fine particles 1, except that the hydrophobizing agent to be used in the above-described "3. Hydrophobizing step" was changed to chlorotrimethylsilane. The physical properties of the obtained fine particles 9 are shown in tables 1-1 to 1-2.

< production example of fine particles 10 >

The fine particles 10 were obtained in the same manner as in the production example of the fine particles 1, except that the hydrophobizing agent to be used in the above-described "3. Hydrophobizing step" was changed to trifluoropropyl trimethoxysilane. The physical properties of the obtained fine particles 10 are shown in tables 1-1 to 1-2.

< production example of fine particles 11 >

The fine particles 11 were obtained in the same manner as in the production example of the fine particles 1, except that the hydrophobizing agent to be used in the above-described "3. Hydrophobizing step" was changed to simethicone. The physical properties of the obtained fine particles 11 are shown in tables 1-1 to 1-2.

< production example of fine particles 12 >

The fine particles 12 were obtained in the same manner as in the production example of the fine particles 1, except that the hydrophobizing agent was not added in the above-described "3. Hydrophobizing step". Physical properties of the obtained fine particles 12 are shown in tables 1-1 to 1-2.

< production example of fine particles 13 >

The fine particles 13 were obtained in the same manner as in the production example of the fine particles 12 except that the amount of dimethyldimethoxysilane was changed to 4.2g in the above-mentioned (1) hydrolysis and polycondensation step "and the amount of tetraethoxysilane was changed to 50.2g in (2). The physical properties of the obtained fine particles 13 are shown in tables 1-1 to 1-2.

< production example of fine particles 14 >

The fine particles 14 were obtained in the same manner as in the production example of the fine particles 12 except that the amount of 28% ammonia water was changed to 3.0g and the stirring temperature was changed to 45 ℃ in the above-described (2) of the "1. Hydrolysis and polycondensation process". The physical properties of the obtained fine particles 14 are shown in tables 1-1 to 1-2.

< production example of fine particles 15 >

The fine particles 15 were obtained in the same manner as in the production example of the fine particles 12 except that the amount of 28% ammonia water was changed to 5.0g and the stirring temperature was changed to 25 ℃ in the above-described (2) of the "1. Hydrolysis and polycondensation process". The physical properties of the obtained fine particles 15 are shown in tables 1-1 to 1-2.

< production example of fine particles 16 >

To a 2,000mL beaker were added 124.0g of ethanol, 24.0g of gRO water, and 10.0g of 28% ammonia water, and the temperature of the solution was adjusted to 70 ℃. Then, both 232.0g of tetraethoxysilane and 84.0g of 5.4% ammonia water were added dropwise to the solution with stirring over 0.5 hours. After the end of the addition, hydrolysis was performed while further continuing stirring for 0.5 hours to thereby provide a dispersion of silicon polymer particles each having a siloxane bond. After 150.0g of hexamethyldisilazane was added to the dispersion of silicon polymer particles each having a siloxane bond obtained in the above procedure at room temperature, the dispersion was heated to 50 to 60 ℃, and then stirred for 3.0 hours. The powder in the dispersion was recovered by suction filtration and dried under reduced pressure at 120 ℃ for 24 hours to thereby provide fine particles 16. The physical properties of the resulting fine particles 16 are shown in tables 1-1 to 1-2.

< production example of fine particles 17 >

Fine particles 17 were obtained in the same manner as in the production example of fine particle 1 except that 54.4g of trimethoxymethylsilane was added instead of dimethyldimethoxysilane in (1) of the above-described "1. Hydrolysis and polycondensation step", the stirring temperature was changed to 30 ℃ and the stirring time was changed to 1.0 hour, and tetraethoxysilane was not added in (2), the amount of RO water was changed to 98.1g, the amount of methanol was changed to 310.7g, the amount of 28% aqueous ammonia was changed to 2.0g and the stirring time was changed to 0.5 hour. Physical properties of the obtained fine particles 17 are shown in tables 1-1 to 1-2.

< production example of fine particles 18 >

The fine particles 18 were obtained in the same manner as in the production example of the fine particles 1 except that the amount of 28% ammonia water was changed to 2.0g and the stirring temperature was changed to 50 ℃ in the above-described (2) of the "1. Hydrolysis and polycondensation process". Physical properties of the obtained fine particles 18 are shown in tables 1-1 to 1-2.

< production example of fine particles 19 >

Fine particles 19 were obtained in the same manner as in the production example of fine particles 1 except that the amount of 28% aqueous ammonia was changed to 6.0g and the stirring temperature was changed to 20 ℃ in the above-described (2) of the "1. Hydrolysis and polycondensation process". The physical properties of the obtained fine particles 19 are shown in tables 1-1 to 1-2.

XA: x value when cutting a test piece made of PET to 20nm

XB: x value at 50nm of PET test piece

YA: y value when a test piece made of PET was cut to 20nm

YB: y value at 50nm cut of PET test piece

< production example of polyester resin A1 >

The above materials were charged into a four-necked 4L flask made of glass, and a thermometer, a stirring bar, a condenser and a nitrogen inlet tube were mounted on the flask. The resulting flask was placed in a jacketed heater. Next, the inside of the flask was purged with nitrogen, and then the temperature was gradually increased with stirring. The materials were allowed to react at 200℃for 4 hours with stirring (first reaction step). Thereafter, 1.2 parts (0.006 mol) of trimellitic anhydride (TMA) was added to the resultant, and the mixture was subjected to a reaction at 180 ℃ for 1 hour (second reaction process), to thereby provide a polyester resin A1 as a binder resin component.

The acid value of the polyester resin A1 was 5mgKOH/g.

< production example of polyester resin A2 >

Polyoxypropylene (2.2) -2, 2-bis (4-hydroxyphenyl) propane 71.3 parts (0.155 mol)

24.1 parts of terephthalic acid (0.145 mol)

Tetrabutyl titanate 0.6 parts

The above materials were charged into a four-necked 4L flask made of glass, and a thermometer, a stirring bar, a condenser and a nitrogen inlet tube were mounted on the flask. The resulting flask was placed in a jacketed heater. Next, the inside of the flask was purged with nitrogen, and then the temperature was gradually increased with stirring. The materials were allowed to react for 2 hours with stirring at a temperature of 200 ℃. Thereafter, 5.8 parts by mass (0.030 mol%) of trimellitic anhydride was added to the resultant, and the mixture was allowed to react at 180 ℃ for 10 hours to thereby provide a polyester resin A2 as a binder resin component. The acid value of the polyester resin A2 was 10mg KOH/g.

< production example of toner particle 1 >

The raw materials shown in the above formulation were mixed with a Henschel mixer (type FM-75, by Nippon Coke)&Engineering co., ltd.) at 20s ^-1 Is mixed at a rotation speed of 5 minutes. Thereafter, the mixture was kneaded with a twin-screw kneader (model PCM-30 manufactured by Ikegai Corporation) set to a temperature of 125 ℃ and a rotational speed of 300 rpm. The obtained kneaded material was cooled and coarsely pulverized with a hammer mill to a diameter of 1mm or less to thereby provide a coarsely pulverized material. The obtained coarsely pulverized material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund-Turbo Corporation). Further, the fine pulverized material was classified with a rotary classifier (200 TSP, manufactured by Hosokawa Micron Corporation) to provide toner particles 1. Rotary classifier (200 TS) P manufactured by Hosokawa Micron Corporation) is as follows: at a rotor speed of 50.0s ^-1 And grading is carried out. The weight average particle diameter (D4) of the resultant toner particles 1 was 5.9. Mu.m.

< production example of toner 1 >

Toner particle 1.100 parts

Fine particles 1.0 part

The above materials were mixed with a Henschel mixer FM-10C (manufactured by Mitsui Miike Machinery Company, limited) for 30s ^-1 Is mixed for a rotation time of 10min to provide the toner particle mixture 1.

(Heat treatment step)

The resulting toner particle mixture 1 was subjected to heat treatment with the surface treatment apparatus shown in fig. 1 to provide a toner 1. Physical properties of the toner 1 are shown in table 2. The operating conditions of the heat treatment were set as follows: the feed rate is 2kg/hr, the hot air temperature is 150deg.C, and the hot air flow rate is 6m ³ The temperature of cold air is-5 ℃ and the flow rate of cold air is 2.5m per minute ³ Per min, the air quantity of the blower is 11m ³ Per min, and the jet air flow is 1m ³ /min。

< production examples of toners 2 to 25 >

Toners 2 to 25 were obtained by carrying out the production in the same manner as in the production example of toner 1 except that the toner particles, the fine particles, the presence or absence of implementation of the hot air treatment process, and the temperature of hot air in the heat treatment process were changed to those shown in table 2. Physical properties of toners 2 to 25 are shown in table 2.

< production example of Carrier 1 >

Magnetite having a number average particle diameter of 0.30 μm (magnetization of 65Am under a magnetic field of 1,000/4 pi (kA/m) ² /kg)

Magnetite having a number average particle diameter of 0.50 μm (magnetization of 65Am under a magnetic field of 1,000/4 pi (kA/m) ² /kg)

4.0 parts of a silane compound (3- (2-aminoethylaminopropyl) trimethoxysilane) was added to each of the above materials, and the mixture was mixed and stirred at high speed at 100℃or higher in a vessel to treat fine particles of each material.

Phenol: 10 mass%

Formaldehyde solution: 6 mass% (40 mass% formaldehyde, 10 mass% methanol, 50 mass% water)

Magnetite treated with the above silane compound: 58 mass%

Magnetite treated with the above silane compound: 26 mass%

The above material, 5 parts of 28 mass% aqueous ammonia solution and 20 parts of water were placed in a flask. While the contents were stirred and mixed, the temperature was raised to 85 ℃ and maintained for 30 minutes to perform polymerization for 3 hours to cure the resultant phenolic resin. Thereafter, the cured phenolic resin was cooled to 30 ℃ and water was added. Thereafter, the supernatant was removed, and the precipitate was washed with water and then air-dried. Then, the air-dried product was dried at a temperature of 60 ℃ under reduced pressure (5 mmHg or less) to provide a magnetic material-dispersed spherical support 1. The 50% particle size (D50) of the support 1 on a volume basis was 34.2. Mu.m.

< production example of two-component developer 1 >

To 92.0 parts of the carrier 1, 8.0 parts of the toner 1 was added, and the contents were mixed with a V-type mixer (V-20 manufactured by Seishin Enterprise co., ltd.) to provide a two-component-system developer 1.

< production example of two-component-based developers 2 to 25 >

The two-component-system developers 2 to 25 were obtained by performing production in the same manner as in the production example of the two-component-system developer 1, except that the toners were changed as shown in table 3.

TABLE 3 Table 3

Two-component developer No.	Toner No.	Vector No.
			Two-component developer 1	Toner 1	Carrier 1
Two-component developer 2	Toner 2	Carrier 1
			Two-component developer 3	Toner 3	Carrier 1
Two-component developer 4	Toner 4	Carrier 1
			Two-component developer 5	Toner 5	Carrier 1
Two-component developer 6	Toner 6	Carrier 1
			Two-component developer 7	Toner 7	Carrier 1
Two-component developer 8	Toner 8	Carrier 1
			Two-component developer 9	Toner 9	Carrier 1
Two-component developer 10	Toner 10	Carrier 1
			Two-component developer 11	Toner 11	Carrier 1
Two-component developer 12	Toner 12	Carrier 1
			Two-component developer 13	Toner 13	Carrier 1
Two-component developer 14	Toner 14	Carrier 1
			Two-component developer 15	Toner 15	Carrier 1
Two-component developer 16	Toner 16	Carrier 1
			Two-component developer 17	Toner 17	Carrier 1
Two-component developer 18	Toner 18	Carrier 1
			Two-component developer 19	Toner 19	Carrier 1
Two-component developer 20	Toner 20	Carrier 1
			Two-component developer 21	Toner 21	Carrier 1
Two-component developer 22	Toner 22	Carrier 1
			Two-component developer 23	Toner 23	Carrier 1
Two-component developer 24	Toner 24	Carrier 1
			Two-component developer 25	Toner 25	Carrier 1

Example 1

< method of evaluating toner >

A remodel machine of a full-color copier imagePRESS C800 manufactured by Canon inc. Was used as the image forming apparatus, and the two-component-system developer 1 was loaded into the developing unit of the cyan station. As a modification point of the apparatus, changes are made so that the fixing temperature and the process speed thereof, the direct-current voltage VDC of the developer bearing member, the charging voltage VD of the electrostatic latent image bearing member, and the laser power can be freely set. The image output evaluation was performed as follows: FFh images (solid images) having a desired image ratio are output and subjected to the later evaluation, wherein VDC, VD, and laser power are adjusted so as to achieve a desired toner bearing amount on the FFh images on the paper.

FFh is a value obtained by expressing 256 gradations in 16 scale; 00h represents the 1 st gray (white background portion) of 256 gray levels, and FFh represents the 256 th gray (solid portion) of 256 gray levels.

The evaluation was performed based on the following evaluation method, and the results are shown in table 4.

(1) Method for evaluating transferability to embossed paper (embossing transferability)

Paper: LEATHAC 66 (302.0 g/m) ² )

(embossed paper manufactured by Tokushu Tokai Paper co., ltd. And obtainable from Tokushu Tokai Paper co., ltd.)

Toner bearing amount on paper: 0.70mg/cm ² (FFh image)

(toner carrying amount on paper by using Mondi color copy paper (250.0 g/m ² ) (available from Mondi plc) based on the direct-current voltage VDC of the developer carrying member, the charging voltage VD of the electrostatic latent image carrying member, and the laser power

Evaluation image: image disposed on the entire surface of A4 paper of LEATHAC 66

Fixing test environment: ambient temperature and humidity (temperature: 23 ℃ C./humidity: 50% RH (hereinafter referred to as "N/N"))

Fixing temperature: 180 DEG C

Treatment speed: 173mm/sec

The evaluation image is output, and the embossing transferability is evaluated. The standard deviation of the brightness was used as an index for evaluating the embossed transferability. The image was read by using a scanner (product name: canoScan 9000F, manufactured by Canon Inc.) at a reading resolution of 1,200dpi under conditions that the image correction process was turned off and that a trimming was performed in the range of 2,550 pixels×2,550 pixels (about 10.8X10.8 cm). Subsequently, a luminance value histogram (vertical axis: frequency (number of pixels)) of the above image data is obtained, and the horizontal axis: luminance, which represents luminance values in the range of 0 to 255. Further, a standard deviation of luminance in the image data is found based on the obtained luminance value histogram. The above test was carried out under an ordinary temperature and ordinary humidity environment (N/N; temperature: 25 ℃, relative humidity: 55%) and an ordinary temperature and low humidity environment (N/L; temperature: 25 ℃, relative humidity: 10%). Classification was performed based on the following criteria, and C or more was judged to be satisfactory. The image processing software "ImageJ" was used to calculate the standard deviation of luminance.

(evaluation criteria: standard deviation of luminance)

A: less than 2.0

B:2.0 or more and less than 4.0

C:4.0 or more and less than 6.0

D:6.0 or more and less than 8.0

E:8.0 or more and less than 10.0

(2) Measurement of image density variation

As evaluation paper, plain paper GF-C081 (A4, basis weight: 81.4g/m was used ² Available from Canon Marketing Japan inc.).

The toner carrying amount on the paper in the FFh image (solid image) was adjusted to 0.45mg/cm ² . First, an image output test of 10,000 sheets was performed at an image rate of 80%And (5) checking. During 10,000 consecutive sheets feeding, the sheet feeding was performed under the same developing condition and transfer condition (not calibrated) as those of the 1 st sheet.

The above test was carried out in a normal temperature and normal humidity environment (N/N; temperature: 25 ℃ C., relative humidity: 55%) and a high temperature and high humidity environment (H/H; temperature: 30 ℃ C., relative humidity: 80%). Measurement of the initial density (1 st sheet) at printing at an image ratio of 80% and the density of the image on the 10,000 th sheet was performed by using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite inc.) and rated based on the following criteria by using the density difference Δ. C or more was judged to be satisfactory.

(evaluation criterion: image concentration difference. DELTA.)

A: less than 0.02

B:0.02 or more and less than 0.05

C:0.05 or more and less than 0.10

D:0.10 or more and less than 0.15

E:0.15 or more

Examples 2 to 21

The two-component-system developers 2 to 21 were evaluated, respectively, in the same manner as in example 1. The evaluation results of examples 2 to 21 are shown in table 4.

Comparative examples 1 to 4

The two-component-system developers 22 to 25 were evaluated, respectively, in the same manner as in example 1. The evaluation results of comparative examples 1 to 4 are shown in table 4.

TABLE 4 Table 4

When the fine particles of the present invention are used as an external additive for toner, the charging stability and durability stability of toner are improved, and the contamination of members by toner is reduced, with the result that high quality images can be stably obtained for a long period of time.

While the invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

Claims

1. A fine particle containing silicon which is formed by a process of forming a fine particle,

characterized in that the number average particle diameter of the primary particles of the fine particles is 0.05 μm or more and 0.20 μm or less,

Wherein, in measurement by X-ray fluorescence XRF, the fine particles contain silicon atoms in a proportion of 20% or more with respect to all elements, and

wherein, regarding the proportion of silicon atoms measured in the case where the fine particles are etched by irradiation with Ar-K alpha rays in analysis by X-ray photoelectron spectroscopy XPS, when the proportion of silicon atoms having the following structure (a) is represented by X and the sum of the proportions of silicon atoms having the following structures (b) to (d) is represented by Y,

2. The fine particles according to claim 1, wherein the X and the Y satisfy a relationship of 0.20+.y/(x+y) at a point in time when a test piece made of PET is cut to a depth of 50nm by irradiation with Ar-ka radiation.

3. The fine particles according to claim 1, wherein the X and the Y satisfy a relationship of 1.2.ltoreq.x/y.ltoreq.2.0 at a point in time when a test piece made of PET is cut to a depth of 50nm by irradiation with Ar-ka radiation.

4. The fine particles according to claim 1, wherein the fine particles are surface-treated with at least one compound selected from the group consisting of alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, and silicone oils.

5. The fine particle according to claim 1, wherein the young's modulus of the fine particle is 10GPa or more and 30GPa or less.

6. The fine particles according to claim 1, wherein, in passing through the fine particles ²⁹ In the graph obtained by Si-NMR measurement, when the total peak area of angelica belonging to the silicon polymer is represented by SA, the peak area ascribed to the structure (a) is represented by S4, the peak area ascribed to the structure (b) is represented by S3 and the peak area ascribed to the structure (c) is represented by S2, the SA, the S2, the S3 and the S4 satisfy the following expressions (I) to (III),

0.30≤S4/SA≤0.80···(I)

0≤S3/SA≤0.50···(II)

0.20≤S2/SA≤0.70···(III)。

7. The fine particles according to claim 1, wherein R in the structures (b) to (d) ₁ 、R ₂ And R is ₃ Each independently represents an alkyl group having 1 to 6 carbon atoms.

8. A toner characterized in that it comprises toner particles and the fine particles according to any one of claims 1 to 7.

9. The toner according to claim 8, wherein the fine particles are contained in an amount of 0.1 parts by mass or more and 20.0 parts by mass or less relative to 100 parts by mass of the toner particles.

10. The toner according to claim 8 or 9, wherein an fixation ratio of the fine particles to the toner particles is 50% or more.