TONER

Abstract

Toner comprising a toner particle, a composite particle present on a surface of the toner particle, and a spherical silicon dioxide particle. The composite particle comprises a particle A containing an organic silicon compound as a binder component, and a particle B, which is an inorganic particle. Particle B is present on a surface of the composite particle in a state where a portion of particle B is embedded within a surface of particle A. The composite particle and the silicon dioxide particle each have a defined particle diameter, the proportions of bifunctional to tetrafunctional silicon atoms in particle A meet specific requirements, and the average embedding ratios of particle B to particle A within the composite particle are 30% or more and 90% or less.

Description

BACKGROUND OF THE INVENTIONField of the InventionThe present disclosure relates to a toner used for an electrophotographic process and a two-component developer formed from the toner.Description of Related ArtIn recent years, with the wide spread use of a full-color electrophotographic copier, there has been a demand for further improvement in image quality and stable output of a high-quality image even in long-term operation. Dot reproducibility must be improved to improve the image quality of the toner, and formation of dense dots upon development is required so that dot collapse does not occur in a transfer step.As a method for improving the dot reproducibility of the toner, there is known a method in which toner particles are coated with spherical silica fine particles to reduce the adhesion force of the toner so that developability and transferability are improved (Japanese Patent Publication No. H 5-72801 and H 8-220874).Further, a method is known in which fine particles in a form in which a plurality of metal oxide particles are embedded in a polymer matrix (base particles) and protrude outward (hereinafter also referred to as a confetti form) are added as an external additive to a surface of a toner to suppress desorption of the external additive from the toner (Japanese Patent No. 5982003).SUMMARY OF THE INVENTIONAs described in Japanese Patent Publication No. H5-72801 and H8-220874, external addition of spherical silica enhances developability and transferability of the toner and also improves dot reproducibility. However, a disadvantage of this method is that when using media with very uneven surfaces, such as rough paper, the pressure is concentrated on protrusions during transfer, which results in the spots collapsing.In a case where the confetti-shaped particles as described in Japanese Patent No. 5982003 are used as an external additive to solve the above-described drawback, confetti-shaped protrusions bite due to the pressure during transfer into the toner, so that the adhesion force between the toner particles is increased and thus suppression of dot collapse can be expected. However, since the adhesion force between the toner particles is increased as compared with a case where a spherical external additive is used, it is difficult to form dense dots due to the adhesion of the confetti-shaped particles even in the developing step where no pressure is applied. Moreover, in confetti-shaped particles formed of resin particles and a metal oxide as described in Japanese Patent No. 5982003, the confetti-shaped particles are embedded in the surface of the toner particles due to long-term use, thereby further degrading dot reproducibility due to a change in state of the particles.The present disclosure provides a toner that overcomes the above-described disadvantages, and more particularly, the present disclosure provides a toner that exhibits satisfactory dot reproducibility even on media having a highly uneven surface such as rough paper from the initial stage to the post-permanent stage.According to the present disclosure, there is provided a toner including: a toner particle; a composite particle present on a surface of the toner particle; and a spherical silica fine particle, the composite particle including a fine particle A containing, as a binder component, an organic silicon compound having a siloxane bond, and a fine particle B being an inorganic fine particle, the fine particle B being present on a surface of the composite particle in a state in which a part of the fine particle B is embedded in a surface of the fine particle A, Since a number average particle diameter of the composite particle is Db is a number average particle diameter of the spherical silica fine particle, Db is 0.03 μm or more and 0.30 μm or less, and 0.4 ≤ Da / Db ≤ 1.8, Pa is a proportion of a silicon atom represented by Si a in a structure represented by a unit (a), Pb is a proportion of a silicon atom represented by Si b in a structure represented by a unit (b), and Pc is a proportion of a silicon atom represented by Si c in a structure represented by a unit (c), with respect to all silicon atoms contained in the organic silicon compound of the fine particle A, and Pa, Pb and Pc satisfy the expressions (1) to (3), (R 1 and R 2 represent an alkyl group having 1 or more and 6 or less carbon atoms), wherein an average value of the embedding ratios of the fine particle B to the fine particle A in the composite particle represented by the following equation is 30% or more and 90% or less.Other features of the present disclosure will become apparent from the following description of exemplary embodiments.DESCRIPTION OF THE EMBODIMENTSIn the present disclosure, the description of a numerical range of "OO or more and XX or less" or "OO to XX" includes a numerical range including the end points as the lower limit and the upper limit unless otherwise specified.Features of the Present DisclosureThe present inventors have presumed the mechanism by which the effects of the present disclosure are exhibited as follows.In a case where spherical silica fine particles and confetti-shaped composite particles containing an organic silicon compound as a binder component are used together as an external additive for a toner, since the portion of the binder of the composite particles is elastic, the portion of the binder of the composite particles is deformed when a pressure is applied thereto, a plurality of protrusions of the composite particles bite into the toner, and as a result, the adhesion force between toner particles is increased. In a state where no pressure is applied to the composite particles, spherical silica is capable of suppressing an increase in adhesion force between toner particles due to protrusions of the composite particles being entangled with each other as in a case where only the composite particles are externally added, and thus the flowability is improved.That is, dense dots can be formed because the flowability is high in the non-printing developing step, and the formed dots can be transferred without collapse because the adhesion force between toner particles increases in the printing transferring step. In addition, since the composite particles contain an organic silicon compound as a binder component, the composite particles have moderate elasticity and are unlikely to be embedded in the toner even after permanent stress, and therefore, the above-described effects are considered to be maintained even after permanent stress.The present disclosure relates to a toner including a toner particle, a composite particle present on a surface of the toner particle as an external additive, and a spherical silica fine particle (hereinafter also referred to as "silica fine particles"), the external additive having the following characteristics. (i) The composite particle includes a fine particle A containing, as a binder component, an organic silicon compound having a siloxane bond and a fine particle B being an inorganic fine particle, and the fine particle B is present on a surface of the composite particle in a state in which a part of the fine particle B is embedded in a surface of the fine particle A. (ii) Da is a number-average particle diameter of the composite particle, Db is a number-average particle diameter of the spherical silica fine particle, Db is 0.03 μm or more and 0.30 μm or less, and 0.4≤Da / Db≤1.8 is satisfied. (iii) Pa is the proportion of a silicon atom represented by Si a in a structure represented by a unit (a), Pb is the proportion of a silicon atom represented by Si b in a structure represented by a unit (b), Pc is the proportion of a silicon atom represented by Si c in a structure represented by a unit (c), with respect to all silicon atoms contained in the organic silicon compound of the fine particle A, and Pa, Pb and Pc satisfy the expressions (1) to (3). ( R 1 and R 2 represent an alkyl group having 1 or more and 6 or less carbon atoms). (iv) An average value of the embedding ratios of the fine particle B to the fine particle A in the composite particle represented by the following equation is 30% or more and 90% or less. External additive (composite particles and silica fine particles)Hereinafter, the configuration of the external additive according to the present disclosure will be described in detail.The number-average particle diameter of the silica fine particles present on the surface of the toner particles according to the present disclosure is 0.03 μm or more and 0.30 μm or less. In a case where the number-average particle diameter is in the above-described range, the toner particles can be uniformly coated with the silica fine particles. In a case where the number-average particle diameter of the silica fine particles is less than 0.03 μm, since the load of the toner increases when a large amount of images having a low printing density is output for a long period of time, the silica fine particles are embedded in the surface of the toner, the adhesion force between the toner particles increases, dense dots cannot be formed in the developing step, and as a result, the dot reproducibility is deteriorated. Further, in a case where the number average particle diameter thereof is larger than 0.30 μm, the silica fine particles are desorbed from the surface of the toner, the adhesion force is increased, and as a result, the dot reproducibility is deteriorated.The number-average particle diameter of the silica fine particles is preferably 0.07 μm or more and 0.20 μm or less, and more preferably 0.08 μm or more and 0.15 μm or less from the above-described viewpoints.Since the number average particle diameter of the composite particles present on the surface of the toner particles of the toner according to the present disclosure is Db is the number average particle diameter of the silica fine particles, and 0.4≤Da / Db≤1.8 is satisfied. When Da / Db is in the above-described range, since the adhesion force between the toner particles in a state where no pressure is applied decreases and the adhesion force between the toner particles in a state where pressure is applied increases, dot reproducibility is improved. In a case where Da / Db is less than 0.4, since the composite particles are extremely large relative to the silica fine particles, the protrusions of the composite particles interlace even in a state where the pressure is not applied, the adhesion force between the toner particles is increased, dense dots cannot be formed in the developing step, and thus the dot reproducibility is deteriorated. Further, in a case where Da / Db is larger than 1.8, since the silica particles are extremely large relative to the composite particles, the effect of the protrusions of the composite particles that wear into the toner is unlikely to be obtained even when the pressure is applied, the effect of increasing the adhesion force between the toner particles when the pressure is applied is weak, and as a result, a dot collapse is likely to occur in the transfer step.Da / Db is preferably 0.5 or more and 1.5 or less, and more preferably 0.7 or more and 1.3 or less from the above-described viewpoint.Pa is the proportion of a silicon atom represented by Si a in a structure represented by the following unit (a), Pb is the proportion of a silicon atom represented by Si b in a structure represented by the following unit (b), Pc is the proportion of a silicon atom represented by Si c in a structure represented by the following unit (c), based on all silicon atoms contained in an organic silicon compound of fine particles A containing the organic silicon compound as a binder component in the composite particles, and Pa, Pb and Pc satisfy the expressions (1) to (3). ( R 1 and R 2 represent an alkyl group having 1 or more and 6 or less carbon atoms).In a case where the values are in the above-described ranges, the fine particles A have moderate elasticity, and thus the initial adhesiveness can be maintained without embedding the fine particles A in the toner even in a case where the stress is applied to the toner from an element such as a carrier due to long-term use. Since the fine particles A are unlikely to be destroyed, the organic silicon compound functions as a binder component for the fine particles B, and the original embedded state of the fine particles B can also be maintained.Pa, Pb and Pc can be controlled by adjusting the amount of a silane monomer having each unit structure to be added. Pa, Pb and Pc may satisfy the expressions (I), (II) and (III), respectively.In the toner according to the present disclosure, the average value of the embedding ratios of the fine particles B represented by the following equation is 30% or more and 90% or less.In a case where the average value of the embedding ratios is in the above-described range, the original embedded state can be maintained because the fine particles B are unlikely to be desorbed from the fine particles A even when the stress is applied to the toner of an element due to long-term use. In a case where the average value of the embedding ratio is less than 30%, since the fine particles B are likely to be desorbed from the fine particles A, the effect of increasing the adhesion force between the toner particles upon application of the pressure is weak. In a case where the average value of the embedding ratios is larger than 90%, the effect of increasing the adhesion force between toner particles when the pressure is applied is weak because the effect that the protrusions bite into the toner when the pressure is applied is unlikely, and therefore the dot collapse is likely to occur in the transfer step.The embedding ratio of the fine particles B can be controlled by adjusting the reaction time and the reaction temperature between the monomer and the fine particles B. When the embedding ratio is to be decreased, a method of decreasing the reaction time between the monomer and the fine particles B or decreasing the reaction temperature may be employed. When the embedding ratio is to be increased, a method of increasing the reaction time between the monomer and the fine particles B or increasing the reaction temperature may be employed. The embedding ratio is preferably 40% or more and 80% or less, and more preferably 45% or more and 70% or less.When Dc is the average height of the portions of the fine particles B protruding from the fine particles A, Dc / Db is preferably 0.03 or more and 0.30 or less. In a case where the average height is in the above-described range, the composite particles have a sufficient protrusion shape with respect to the silica fine particles, and thus the effect that the protrusions bite into the toner when the pressure is applied can be obtained. Dc / Db is more preferably 0.05 or more and 0.20 or less from the above-described viewpoint.In a case where A D is the number-average primary particle diameter of the fine particles A and B D is the number-average particle diameter of the primary particles of the fine particles B, B is D / A D preferably 0.05 or more and 0.70 or less. When B D / A D is in the above-described range, there can be obtained the effect that the flowability is not lowered when the pressure is not applied to the composite particles, and the protrusions bite into the toner when the pressure is applied thereto. B D / A D is more preferably 0.10 or more and 0.50 or less from the above-described viewpoint.The Young's modulus of the fine particles B is preferably 50 GPa or more. When the Young's modulus is in the above-described range, the effect can be obtained that the protrusions wear out when the pressure is applied to the toner. The Young's modulus of the fine particles B is more preferably 60 GPa or more than the above-described value.The content of the composite particles and the content of the silica fine particles based on 100 parts by mass of the toner particles are preferably 0.10 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 15.0 parts by mass or less, and even more preferably 1.0 parts by mass or more and 10.0 parts by mass or less. When the content of the composite particles and the content of the silica fine particles is less than 0.1 parts by mass, the flowability of the toner is extremely low, and therefore dense dots are unlikely to be formed in the developing step. In addition, when the content of the composite particles and the content of the silica fine particles are more than 20.0 parts by mass, filming of external additive particles may occur on a support, a charging member, and a photosensitive member when images are output for a longer period of time.Further, the ratio (content of composite particles with respect to 100 parts by mass of toner particles) / (content of silica fine particles with respect to 100 parts by mass of toner particles) is preferably 0.2 or more and 5.0 or less. When the ratio is in the range described above, there can be obtained the effect that the adhesion force between the toner particles decreases when no pressure is applied and the adhesion force between the toner particles increases when the pressure is applied. The above-described ratio (composite particle content / silica fine particle content) is more preferably 0.5 or more and 2.0 or less from the above-described viewpoint.The fine particles B may be silica. When the silica fine particles are, the fine particles B have moderate hardness, and thus the effect that the protrusions of the composite particles wear out upon application of the pressure into the toner can be obtained. When the fine particles B are silica, the chargeability of silica fine particles added separately from the composite particles is similar to that of the fine particles B, and therefore the charge distribution of the toner is likely to be uniform, and developability and transferability are improved.The silica fine particles used in the present disclosure are particles containing silica (i.e., SiO 2) as a main component, and may be particles prepared using a silicon compound such as water glass or alkoxysilane as a raw material, or particles obtained by pulverizing quartz.Specific examples thereof include silica particles prepared by a sol-gel method, precipitated silica particles prepared by a precipitation method, aqueous colloidal silica particles, fumed silica particles obtained by a gas phase method, and fused silica particles. Among these, from the viewpoint of reactivity with the above-described binder component and dispersion stability, aqueous colloidal silica particles are preferred. The aqueous colloidal silica particles are commercially available or can be prepared from various starting materials by a known method. The aqueous colloidal silica particles can be made of silica derived from an alkali silicate solution having a pH of about 9 to 11, and silicate anions are polymerized to produce silica particles having a desired average particle diameter in the form of an aqueous dispersion liquid.The true specific gravity of the composite particles is preferably 1.00 g / cm 3 or more and 1.60 g / cm 3 or less. In a case where the true specific gravity is in the above-described range, since the amount of the fine particles B with respect to the fine particles A is appropriate, the effect of increasing the adhesion force between the toner particles upon application of the pressure can be obtained, and the composite particles are unlikely to be embedded in the toner due to the moderate elasticity, even in the case of long-term use. The true specific gravity is more preferably 1.20 g / cm 3 or more and 1.50 g / cm 3 or less from the above-described viewpoint.The surface of the composite particles and the silica fine particles may be subjected to surface treatment with a hydrophobic treatment agent. The hydrophobic treating agent is not particularly limited, but an organic silicon compound is preferred. Examples thereof include an alkyl silazane compound such as hexamethyldisilazane, an alkylalkoxysilane compound such as diethyldiethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane or butyltrimethoxysilane, a fluoroalkylsilane compound such as trifluoropropyltrimethoxysilane, a chlorosilane compound such as dimethyldichlorosilane or trimethylchlorosilane, a siloxane compound such as octamethylcyclotetrasiloxane, silicone oil, and silicone varnish.In addition, the composite particles and the silica fine particles may be subjected to surface treatment with the same hydrophobic treatment agent. When the composite particles and the silica fine particles are subjected to surface treatment using the same hydrophobic treatment agent, dense dots can be formed in the developing step because the adhesion force between the toner particles decreases when the print is not applied. Among the above-described examples, the composite particles and the silica fine particles may be subjected to surface treatment with at least one compound selected from the group consisting of an alkyl silazane compound, an alkylalkoxysilane compound, a chlorosilane compound, a siloxane compound, and silicone oil. Further, the composite particles and the silica fine particles may be subjected to surface treatment with an alkyl silazane compound from the above-described viewpoint.The Young's modulus of the composite particles is preferably 10 GPa or more and 30 GPa or less. When the Young's modulus of the composite particles is in the above-described range, the composite particles are unlikely to be embedded in the toner even in long-term use because the composite particles have moderate elasticity, and thus the initial adhesion force can be maintained. Method for Producing Composite ParticlesThe method for producing the composite particles according to the present disclosure is not particularly limited, but the composite particles may be formed by hydrolysis and a polycondensation reaction of a silicon compound (silane monomer) using a sol-gel method. More specifically, the composite particles can be formed by hydrolyzing and polycondensation of a mixture of bifunctional silane having two siloxane bonds, trifunctional silane having three siloxane bonds and tetra-functional silane having four siloxane bonds, and reacting the mixture with low-resistance fine particles (corresponding to fine particles B). The silane monomers such as the bifunctional silane, the trifunctional silane and the tetra-functional silane are described below. The proportion of the bifunctional silane is preferably 30 mol % or more and 70 mol % or less, the proportion of the trifunctional silane is preferably 50 mol % or less, and the proportion of the tetravalent silane is preferably 30 mol % or more and 80 mol % or less.The composite particles according to the present disclosure mainly include the fine particles A containing a silicon compound having siloxane bond as a binder.A method for producing the silicon compound is not particularly limited, and the silicon compound can be obtained, for example, by adding a silane compound dropwise to water to conduct hydrolysis and condensation reaction using a catalyst and filtering and drying the obtained suspension. The particle diameter can be controlled by adjusting the kind of the catalyst, the mixing ratio, the reaction start time, the dropping time, and the like. Examples of the catalyst include an acidic catalyst such as hydrochloric acid, hydrofluoric acid, sulfuric acid or nitric acid, and a basic catalyst such as ammonia water, sodium hydroxide or potassium hydroxide, but the present disclosure is not limited thereto.The silicon compound can be produced by the following method. More specifically, the method may include a first step of obtaining a hydrolyzate of a silicon compound, a second step of mixing the hydrolyzate, an alkaline aqueous medium and a dispersion liquid of low resistance particles to cause a polycondensation reaction of the hydrolyzate so that the hydrolyzate reacts with the low resistance particles, and a third step of mixing the polycondensation reactant with an aqueous solution to form particles. In some cases, a hydrophobicizing agent may be additionally added to the mixture.In the first step, a silicon compound and a catalyst are contacted with each other, for example, by a method in which the silicon compound and the catalyst are stirred or mixed in an aqueous solution obtained by dissolving an acidic or alkaline substance serving as a catalyst in water. As the catalyst, a known catalyst can be suitably used. Specific examples of the catalyst include an acidic catalyst such as acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid or nitric acid, and a basic catalyst such as ammonia water, sodium hydroxide or potassium hydroxide.The amount of the catalyst to be used can be suitably adjusted according to the kinds of the silicon compound and the catalyst. The amount may be set to be in a range of 1×10 -3 parts by mass or more and 1 part by mass or less, based on 100 parts by mass of the amount of water used in the case of hydrolysis of the silicon compound.When the amount of the catalyst to be used is 1×10 -3 parts by mass or more, the reaction sufficiently proceeds. In a case where the amount of the catalyst to be used is 1 part by mass or less, the concentration of the catalyst remaining as an impurity in the fine particles is reduced, so that the hydrolysis can be easily performed. The amount of the water to be used is preferably 2 mol or more and 15 mol or less based on 1 mol of the silicon compound. The hydrolysis reaction sufficiently proceeds when the amount of water is 2 mol or more, and productivity is improved when the amount of water is 15 mol or less.The reaction temperature is not particularly limited, and the reaction may be carried out at room temperature or in a heated state, but the reaction may be carried out in a state in which the temperature is maintained at 10° C. to 60° C., from the viewpoint of obtaining a hydrolyzate in a short time and suppressing a partial condensation reaction of the produced hydrolyzate. 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 a reaction solution obtained by bringing the silicon compound, an acid and water into contact, and productivity.In a method for producing silicon polymer particles, the raw material solution obtained in the above-described first step is mixed with an alkaline aqueous medium to cause a polycondensation reaction of a particle precursor in a second step. Thus, a polycondensation reaction solution is obtained. The alkaline aqueous medium here is a liquid obtained by mixing an alkaline component, water and optionally an organic solvent.The alkaline component used in the alkaline aqueous medium is a component whose aqueous solution is basic and which serves as a neutralizer for the catalyst used in the first step and also as a catalyst for the polycondensation reaction in the second step. Examples of such an alkaline component include an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide, ammonia, and organic amines such as monomethylamine and dimethylamine.The amount of the alkaline component to be used is an amount thereof used to neutralize an acid and effectively function as a catalyst of the polycondensation reaction, and for example, in a case where ammonia is used as the alkaline component, the amount thereof is selected to be in a range of typically 0.01 parts by mass or more and 12.5 parts by mass or less with respect to 100 parts by mass of a mixture of water and an organic solvent.In the second step, in addition to the alkaline component and water, an organic solvent may be used to prepare the alkaline aqueous medium. The organic solvent is not particularly limited as long as it is compatible with water, but an organic solvent which dissolves at room temperature and normal pressure at least 10 g of water per 100 g of the organic solvent is suitable.Specific examples of the organic solvent include alcohol such as methanol, ethanol, n-propanol, 2-propanol or butanol, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, or hexanetriol, ethers such as ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, or diacetone alcohol, and an amide compound such as dimethylformamide, dimethylactamide, or N-methylpyrrolidone.Among the above-described organic solvents, an alcohol-based solvent such as methanol, ethanol, 2-propanol or butanol is preferable. In addition, from the standpoints of hydrolysis and dehydration condensation reaction, it is preferable to use, as the organic solvent, the same alcohol as the alcohol generated by desorption.In a third step, the polycondensation reactant obtained in the second step is mixed with an aqueous solution to form particles. As the aqueous solution, water (tap water, pure water or the like) can be suitably used, and a component compatible with water such as a salt, an acid, an alkali, an organic solvent, a surfactant or a water-soluble polymer may be additionally added to the water. The temperature of the polycondensation reaction solution and the aqueous solution in the mixed state is not particularly limited, and is appropriately selected in a range of 5° C. to 70° C. in consideration of the compositions, productivity, and the like.A known method can be used as a method for recovering particles without particular limitation. Examples of such a method include a floating powder scooping method and a filtration method. Among these methods, a filtration method is preferred from the viewpoint of easy handling. The filtration method is not particularly limited, and vacuum filtration, centrifugal filtration, pressure filtration, or the like can be performed by selecting a known device. The filter paper, the filter, the filter cloth and the like used in the filtration are not particularly limited as long as they are industrially available, and can be appropriately selected depending on the apparatus to be used.The monomer to be used may be selected depending on the compatibility with the solvent and the catalyst, the hydrolyzability and the like. Examples of tetra-functional silane monomers having the structure represented by the unit (a) include tetramethoxysilane, tetraethoxysilane, and tetraisocyanatosilane. Among these, tetraethoxysilane is preferred.Examples of the trifunctional silane monomer having the structure represented by the unit (b) include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxysilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, Propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane. Among these, methyltrimethoxysilane is preferred.Examples of the bifunctional silane monomer having the structure represented by the unit (c) include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and diethyldimethoxysilane. Among these, dimethyldimethoxysilane is preferred. Silica Fine Particles and Methods for Producing SameExamples of the silica fine particles include particles formed of silica, such as wet silica obtained by a sedimentation method, a sol-gel method or the like, and dry silica obtained by a deflagration method, a pyrogenic method or the like, with dry silica being preferred from the viewpoint of easy control of the shape. Further, the concept of the silica fine particles according to the present disclosure includes particles obtained by performing hydrophobic treatment of the silica with a hydrophobic treatment agent. The dry silica is formed from a silicon halide compound or the like as a raw material. As the silicon halide compound, silicon tetrachloride is used, but silanes such as methyltrichlorosilane and trichlorosilane may be used alone or silicon tetrachloride and silanes in a mixed state may be used as a raw material. After evaporation of the raw material, the target silica is obtained by a so-called flame hydrolysis reaction in which the raw material reacts with water produced as an intermediate product in a oxyhydrogen flame. For example, a thermal decomposition-oxidation reaction of silicon tetrachloride gas into oxygen and hydrogen is used, and the reaction formula is as follows. SiCl 4+ 2 H 2+ O 2 → SiO 2+ 4 HClA process for producing dry silica will be described below. Oxygen gas is supplied to a burner to ignite the ignition burner, hydrogen gas is supplied to the burner to form a flame, and silicon tetrachloride, which is a raw material, is added for gasification. Then, a flame hydrolysis reaction is carried out and the produced silica powder is recovered. The average particle diameter and the shape can be arbitrarily set by appropriately changing the flow rate of silicon tetrachloride, the flow rate of oxygen supply, the flow rate of hydrogen supply, and the residence time of silica in the flame. The silica fine particles can be subjected to hydrophobic treatment. As the hydrophobic treatment agent, a silicon compound, silicone oil or a mixture thereof may be used, but the hydrophobic treatment may be carried out with only a silicon compound from the viewpoint of obtaining excellent dispersibility of the inorganic fine particles.Components of the toner particlesHereinafter, the constituent materials of the toner particles according to the present disclosure will be described in detail.Binder resinThe binder resin used in the toner according to the present disclosure is not particularly limited, and the following polymer or resin may be used as the binder resin.Examples of binder resins include homopolymers of styrene and its substituents such as poly-p-chlorostyrene and polyvinyl toluene; styrene-based copolymers such as a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, a styrene-acrylic ester copolymer, a styrene-methacrylic ester copolymer, a styrene-α-methylchloromethacrylate copolymer, a styrene-acrylonitrile copolymer, a styrene-vinylmethyl ether copolymer, a styrene-vinylethyl ether copolymer, a styrene-vinylmethyl ketone copolymer, and a styrene-acrylonitrile-indene copolymer; Polyvinyl chloride, a phenol resin, a natural modified phenol resin, a natural resin modified maleic acid resin, an acrylic resin, a methacrylic resin, polyvinyl acetate, a silicone resin, a polyester resin, polyurethane, a polyamide resin, a furan resin, an epoxy resin, a xylene resin, polyvinyl butyral, a terpene resin, a cumarone-indene resin, and a petroleum-based resin. Among them, a polyester resin is preferred from the viewpoint of durability and charge stability.Further, the acid value of the polyester resin is preferably 0.5 mg / g or more and 40 mgKOH / g or less from the viewpoint of environmental stability and charging stability. The acid value in the polyester resin and Si-CH 3 in the fine particles interact with each other, whereby durability and toner chargeability in a high-temperature and high-humidity environment can be further improved. The acid value is more preferably 1 mg / g or more and 20 mgKOH / g or less, and even more preferably 1 mgKOH / g or more and 15 mgKOH / g or less.Coloring AgentThe toner according to the present disclosure may contain a coloring agent as needed. Examples of the colorant are described below.Examples of a black colorant include carbon black and a colorant tinted black using a yellow, a magenta, and a cyan colorant. A pigment may be used alone in the colorant, but a colorant obtained by combining a dye and a pigment with improved sharpness is preferred from the viewpoint of image quality of a full color image.Examples of a pigment for a magenta toner include 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, and 282; C.I. Pigment Violet 19; C.I. Violet 1, 2, 10, 13, 15, 23, 29, and 35.Examples of a dye for a magenta toner include C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109 and 121; C.I. Disperse Red 9; C.I. Solvent Violet 8, 13, 14, 21 and 27; an oil-soluble dye such as C.I. Disperse Violet 1, 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 and 40; and a basic dye such as C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27 and 28.Examples of a pigment for a cyan toner include C.I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16 and 17; C.I. Vat Blue 6; C.I. Acid Blue 45; and a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted by a phthalocyanine skeleton.Examples of a dye for a cyan toner include C.I. Solvent Blue 70.Examples of a pigment for a yellow toner include 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, and 185; and C.I. Vat Yellow 1, 3, and 20.Examples of a dye for a yellow toner include C.I. Solvent Yellow 162.The content of the colorant is preferably 0.1 parts by mass or more and 30.0 parts by mass or less based on 100 parts by mass of the binder resin.WaxThe toner according to the present disclosure may use wax as needed. Examples of the wax include hydrocarbon-based wax such as microcrystalline wax, paraffin wax or Fischer-Tropsch; an oxide of hydrocarbon-based wax such as oxidized polyethylene wax or a block copolymer thereof; waxes containing fatty acid esters as a main component such as carnauba wax; and waxes obtained by partially or completely deoxidizing fatty acid esters such as deoxidized carnauba wax.Other examples of the wax include straight chain saturated fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid and parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauba alcohol, ceryl alcohol and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauba alcohol, ceryl alcohol and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylene bisstearamide, ethylene biscapricamide, ethylene bislauramide, and hexamethylene bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'-dioleyladipamide, and N,N'-dioleylsebacamide; aromatic bisamides such as m-xylene bistaearamide and N,N'-distearyl isophthalamide; aliphatic metal salts (commonly known as a metal soap) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted to an aliphatic hydrocarbon wax using a vinyl-based monomer such as styrene or acrylic acid; a partially esterified polyhydric alcohol-fatty acid substance such as behenic acid monoglyceride; and a methyl ester compound containing a hydroxyl group and obtained by hydrogenating vegetable fats and oils.The content of the wax is preferably 2.0 parts by mass or more and 30.0 parts by mass or less based on 100 parts by mass of the binder resin.Charge Control AgentThe toner according to the present disclosure may also contain a charge control agent, if necessary. As the charge control agent in the toner, a known charge control agent can be used, but particularly preferred is an aromatic carboxylic acid metal compound which is colorless, has a high charging speed, and stably maintains a constant charge amount.Examples of a negative charge control agent include a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, a polymer type compound having a sulfonic acid or a carboxylic acid in a side chain, a polymer type compound having a sulfonate or a sulfonic acid esterified substance in a side chain, a polymer type compound having a carboxylate or a carboxylic acid esterified substance in a side chain, a boron compound, a urea compound, a silicon compound, and a calixarene. The charge control agent may be added internally or externally to the toner particles.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, based on 100 parts by mass of the binder resin.Inorganic fine powderIn addition to the above-described fine particles, other inorganic fine particles may also be used in the toner according to the present disclosure, as needed. The inorganic fine particle may be internally added to the toner particles or mixed as an external additive with the toner base particles. Inorganic fine powder is preferably used as an external additive. The inorganic fine powder may be hydrophobicized with a hydrophobicizing agent such as a silicon compound, silicone oil, or a mixture thereof.Inorganic fine powder having a specific surface area of 50 m 2 / g or more and 400 m 2 / g or less is preferable as an external additive for improving flowability. Inorganic fine powders having specific surfaces in the above-described range can also be used in combination to both improve flowability and stabilize durability. The content of the inorganic fine particle is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, based on 100 parts by mass of the toner particles. When the content is in the above-described range, the effect of the stableness is more likely to be obtained.DeveloperThe toner according to the present disclosure can be used as a one-component developer, but the toner can be mixed with a magnetic carrier and used as a two-component developer to further improve dot reproducibility from the viewpoint of obtaining an image stabilized over a long period of time. That is, the two-component developer may contain a toner and a magnetic carrier, and the toner may be the toner according to the present disclosure.Examples of magnetic carriers include well-known magnetic carriers such as surface oxidized iron powder, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium and rare earths, their alloy particles, oxide particles, a magnetic material such as ferrite, and a magnetic material dispersing resin carrier (so-called resin carrier) containing a magnetic substance and a binder resin which maintains the magnetic material in a dispersed state.In a case where the toner is mixed with the magnetic carrier and used as a two-component developer, satisfactory results can be generally obtained when the mixing ratio of the carrier is adjusted to preferably 2 mass % or more and 15 mass % or less, and preferably 4 mass % or more and 13 mass % or less with respect to the concentration of the toner in the two-component developer. Method for Producing Toner Particles and Method for Producing TonerA method for producing the toner particles is not particularly limited, and a known prior art production method such as a suspension polymerization method, an emulsion aggregation method, a melt kneading method, or a solution suspension method can be used.The toner can be obtained by mixing the obtained toner particles with inorganic fine particles and, optionally, other external additives. The toner particles can be mixed with the inorganic fine particles and other external additives using a device such as a double cone mixer, a V mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, Mechano Hybrid (manufactured by NIPPON COKE & ENGINEERING CO., LTD.), or NOBILTA (manufactured by Hosokawa Micron Corporation). Method for Measuring Various Physical PropertiesMethods for measuring various physical properties will be described below. Separation of Fine Particles and Toner Particles from TonerEach physical property can be measured from the fine particles separated from the toner by the following method.To prepare a concentrated sucrose solution, 200 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 ml of ion exchange water and dissolved in a hot water bath. 31 g of the concentrated sucrose liquid and 6 ml of contaminon N (10 mass % aqueous solution for a neutral detergent for cleaning a precision meter consisting of a nonionic surfactant, an anionic surfactant and an organic builder and having a pH of 7, manufactured by FUJIFILM Wako Pure Chemical Corporation) are placed in a centrifuge tube to prepare a dispersion liquid. To the dispersion liquid, 1 g of toner is added, and the lumps of toner are loosened with a spatula or the like.The centrifuge tube is shaken in a shaker for 20 minutes, with a reciprocating motion occurring 350 times per minute. After shaking, the solution is transferred to a glass tube (50 mL) for a swing rotor and centrifuged for 30 minutes in a centrifuge at 3500 U / min. In the glass tube after centrifugation, the toner is on the uppermost layer and the fine particles on the lower layer on the aqueous solution side. The aqueous solution on the lower layer is collected and centrifuged to separate the sucrose and the fine particles, and the fine particles are collected. The centrifugation is repeated as many times as necessary for sufficient separation, the dispersion liquid is dried, and the fine particles are collected.In a case where a plurality of external additives are added, the external additive according to the present disclosure may be sorted out by a centrifugal separation method or the like. Method for Measuring Number-Average Primary Particle Diameter of External AdditiveThe number-average primary particle diameter of the external additive can be determined by measurement by a centrifugal sedimentation method. Specifically, 0.01 g of the dried external additive particles are placed in a 25 mL glass vial and a solution prepared by adding 0.2 g of a 5% Triton solution and 19.8 g of RO water to the particles. Subsequently, a probe (tip in the tip) of an ultrasonic disperser is immersed in the solution and ultrasonically dispersed at a power of 20 W for 15 minutes, thereby obtaining a dispersion liquid. Subsequently, with this dispersion liquid, the number-average primary particle diameter of the particles is measured with a centrifugal sedimentation particle size distribution measuring apparatus DC24000 (manufactured by CPS Instruments, Inc.). The rotational speed of a disc is set to 18000 U / min and the true density to 1.3 g / cm 3. Prior to measurement, the apparatus is calibrated with polyvinyl chloride particles having an average particle diameter of 0.476 μm.Method for Measuring Embedding Ratio of Fine Particles BThe external additive is sufficiently dispersed in a visible light curable resin (trade name ARONIX LCR Series D-800, manufactured by TOAGOSEI CO., LTD.), and the resin is irradiated with short-wave light and cured. The obtained cured substance is cut out with an ultramicrotome provided with a diamond knife to prepare a scale-shaped sample having a size of 250 nm. Then, the cut-out sample is magnified (TEM-EDX) at 40000 to 5000 times magnification with a transmission electron microscope (electron microscope JEM-2800 manufactured by JEOL Ltd.), and a cross section of the external additive is observed. The diameter of the fine particles B and the depth of the fine particles B embedded in the fine particles A are measured from the cross-sectional image. Five fine particles B are randomly selected per particle of the external additive, and the embedding ratio of the fine particles B is calculated according to the following equation. Further, the number of the particles of the external additive to be analyzed is set to 20 or more particles, and the average value of the obtained embedding ratios is defined as the embedding ratio of the fine particles B.Embedding ratio (%) of fine particles B = (depth of embedding of fine particles B into fine particles A / diameter of fine particles B) × 100 Method for measuring B D / A D of the external additiveA cross section of the external additive is viewed according to the method described above to calculate B D / A D of the external additive. The particle diameters of the fine particles A and the fine particles B are calculated from the image obtained by the observation. As the number of the particles to be analyzed, the number of the particles of the external additive is set to 20 particles, and the average value thereof is defined as the value of B D / A D in the present disclosure.Method for measuring the content ratio of the constituent compound in the external additive according to solid state 29Si-NMRIn the solid state 29 Si-NMR, peaks in various shift ranges are detected by the structure of the Si-bonded functional group of the constituent compound of the external additive. The structure bonded to Si can be determined by specifying each peak position from a standardized sample. From the obtained peak area, the ratio of the frequency of the individual constituent compounds can then be calculated. The ratios of the peak areas of an M unit structure, a D unit structure (c), a T unit structure (b), and a Q unit structure (a) with respect to the entire peak area can be obtained by calculation.Specifically, the measurement conditions for the solid state 29 Si-NMR are as follows.Device: JNM-ECX5002 (JEOL RESONANCE)Temperature: room temperatureMeasurement method: DDMAS method 29Si 45°Sample tube: Zirconia 3.2 mmφSample: Sample tube filled with the sample in powder form Sample rotation speed: 10 kHzRelaxation retardation: 180 secScan: Scan: 2000After the measurement, a plurality of silane components of the sample having different substituents and bonding groups are separated into peaks of the following M unit structure, D unit structure (c), T unit structure (b) and Q unit structure (a) by curve fitting, and each peak area is calculated.The curve fitting is performed with EXcalibur for Windows (registered trademark) version 4.2 (EX series) for the software JNM-EX400 (manufactured by JEOL Ltd.). The measurement data is read in by clicking on "1D Pro" in the menu symbols. Then, in the menu bar under "Command", the function "curve fitting function" is selected, and the curve fitting is performed. The curve fitting for each component is performed so as to minimize a difference (difference of synthesized peaks) between a synthesized peak formed by the synthesis of each peak obtained by the curve fitting and a peak that is the measurement result.M unit structure: (Ra)(Rb)(Rc)SiO 1 / 2D unit structure: (Rd)(Re)Si(O 1 / 2)2( c)T Unit Structure: RfSi(O 1 / 2)3( b)Q unit structure: Si(O 1 / 2)4( a)Ra, Rb, Rc, Rd, Re and Rf in the above formulae represent an organic group (e.g., an alkyl group or an alkoxy group) such as a hydrocarbon group having 1 or more and 6 or less carbon atoms bonded to silicon, a halogen atom or a hydroxy group. The content proportions of (a), (b) and (c) in the external additive are calculated from the peak area corresponding to the structure represented by formula (a), the peak area corresponding to the structure represented by formula (b), and the peak area corresponding to the structure represented by formula (c), which are obtained by the measurement. Further, in a case where the structures need to be confirmed in more detail, the measurement results of 13 C-NMR and 1 H-NMR can be identified together with the measurement results of 29 Si-NMR. Method for Measuring True Specific Gravity of External AdditiveThe true specific gravity of the external additive is measured with an automatic dry type densitometer AUTOPYCNOMETER (manufactured by Yuasa Ionics Co., Ltd.). The conditions for the measurement are as follows.Cell: SM cell (10 mL)Sample quantity: 0.05 gThis measurement method is a method for measuring the true specific gravity of a solid and a liquid using a gas phase substitution method.Similar to a liquid phase substitution method, this method is based on the Archimedes principle, but has high precision for micropores because gas (argon gas) is used as a substitution medium. Method for Measuring External Additive Surface Treatment AgentA surface treatment agent of the external additive is analyzed by pyrolysis GC-MS (gas chromatography-mass spectrometry).The specific measurement conditions are as follows.Apparatus: GC6890A (manufactured by Agilent Technologies), Pyrolyzer(Manufactured by Japan Analytical Industry Co., Ltd.)Column: HP-5ms 30mPyrolysis temperature: 590° CThe surface treatment agent of the external additive is specified by specifying each peak position of the profile obtained by the measurement with a standard sample.Method for Measuring the Young's Modulus of Composite ParticlesThe Young's modulus of the composite particles is determined by a microcompression test conducted with a Hysitron PI 85L picoindenter (manufacturer BRUKER). The Young's modulus (MPa) is calculated from the slope of the profile (load-displacement curve) of the displacement (nm) and the test force (μN) obtained by the measurement.Device and JigBasic system: Hysitron PI-85LMeasuring mandrel: Circular, flat end mandrel with a diameter of 1 μmUsed SEM: Thermo Fisher Versa 3DConditions for SEM: -10° tilt, 13 pA at 10 keV- Measurement conditionsMeasurement mode: Displacement controlMaximum shift: 30 nmDisplacement rate: 1 nm / secRetention time: 2 secondsDischarge rate: 5 nm / sec- Analytical methodHertzian analysis is applied to the curve when the obtained load displacement curve is compressed by 0 nm to 10 nm, and the Young's modulus of the composite particles is calculated.- Sample settingA sample is prepared by attaching the composite particles to a silicon wafer.Method for Measuring Young's Modulus of Fine Particles BFirst, the composition of the fine particles B is identified. The measurement is performed with a scanning electron microscope "S-4800" (trade name, manufactured by Hitachi, Ltd.). An external additive in which a contrast difference of an image occurs between a location derived from the fine particles B as an inorganic substance and a location derived from the fine particles A as an organic substance is defined as an external additive for the toner according to the present disclosure, and an external additive in which the contrast difference has not occurred is defined as another external additive as the external additive for the toner according to the present disclosure. Further, it is observed that the fine particles B as the inorganic substance have higher brightness. The external additives are considered, and the compositions of the fine particles A and the fine particles B are identified with an energy dispersive X-ray analyzer in a field of view enlarged to a maximum of 20000. The composition of the fine particles B is identified, fine particles having the same composition as the composition of the fine particles B are prepared, the Young's modulus of the fine particles is measured in the same manner as the measurement of the Young's modulus of the above-described composite particles, and the obtained value is defined as the Young's modulus of the fine particles B.ExamplesHereinafter, the present disclosure will be described in more detail by way of examples. However, the present disclosure is not limited to these. In the following formulations, unless otherwise indicated, the "parts" refer to the mass.Production Example of Composite Particles 11. Hydrolysis and polycondensation step(1) A 500 mL beaker was charged with 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst and 12.2 g of dimethyldimethoxysilane, and the mixture was stirred at 45° C. for 5 minutes.(2) 2,0 g of 28% ammonia water, 15.0 g of tetraethoxysilane, and 5.0 g of a colloidal silica aqueous dispersion liquid A (silica solid content: 40% by mass, particle diameter of 30 nm) were added thereto, and the mixture was stirred at 30° C. for 3.0 hours, thereby obtaining a raw material solution.2. Granulation step120,0 g of RO water was placed in a 1000 mL beaker, and the raw material solution obtained in Step 1 was added dropwise thereto for 5 minutes while the mixture was stirred at 25° C. Thereafter, the mixed solution was heated to 60°C and stirred for 1.5 hours while the temperature of the solution was maintained at 60°C, whereby a dispersion liquid of the composite particles was obtained.3. Hydrophobization step6,0 g of hexamethyldisilazane as a hydrophobicizing agent was added to the dispersion liquid of the composite particles obtained in the above-described 2nd granulation step, and the solution was stirred at 60° C. for 3.0 hours. The solution was allowed to stand for 5 minutes, and the powder precipitated in the lower portion of the solution was recovered by suction filtration and dried at 120°C for 24 hours under reduced pressure to obtain Composite Particles 1. The physical properties of the obtained composite particles 1 are shown in Table 1. Production Example of Composite Particles 2Composite particles 2 were obtained in the same manner as in the preparation example of composite particles 1, except that the amount of dimethyldimethoxysilane in the item (1) of the 1st hydrolysis and polycondensation step described above was changed to 7.2 g and the amount of tetraethoxysilane in the item (2) was changed to 20.0 g. The physical properties of the obtained composite particles 2 are shown in Table 1. Production Example of Composite Particles 3Composite particles 3 were obtained in the same manner as in the preparation example of composite particles 1, except that the amount of dimethyldimethoxysilane in the item (1) of the 1st hydrolysis and polycondensation step described above was changed to 14.5 g and the amount of tetraethoxysilane in the item (2) was changed to 12.7 g. The physical properties of the obtained composite particles 3 are shown in Table 1. Production Example of Composite Particles 4Composite particles 4 were obtained in the same manner as in the preparation example of composite particles 1, except that the amount of dimethyldimethoxysilane in the item (1) of the 1st hydrolysis and polycondensation step described above was changed to 16.0 g and the amount of tetraethoxysilane in the item (2) was changed to 11.2 g. The physical properties of the obtained composite particles 4 are shown in Table 1. Production Example of Composite Particles 5Composite particles 5 were obtained in the same manner as in the preparation example of composite particles 1, except that the amount of dimethyldimethoxysilane in the item (1) of the 1st hydrolysis and polycondensation step described above was changed to 19.2 g and the amount of tetraethoxysilane in the item (2) was changed to 8.0 g. The physical properties of the obtained composite particles 5 are shown in Table 1. Production Example of Composite Particles 6Composite particles 6 were obtained in the same manner as in the preparation example of composite particles 1, except that the amount of dimethyldimethoxysilane in the item (1) of the 1st hydrolysis and polycondensation step described above was changed to 5.0 g, and in the item (2), the amount of tetraethoxysilane was changed to 10.2 g, and 12.0 g of trimethoxymethylsilane was added. The physical properties of the obtained composite particles 6 are shown in Table 1. Production Example of Composite Particles 7Composite particles 7 were obtained in the same manner as in the production example of composite particles 1, except that 27.2 g of trimethoxymethylsilane was added instead of dimethyldimethoxysilane in the item (1) of the above-described 1st hydrolysis and polycondensation step, and tetraethoxysilane in the item (2) thereof was not added. The physical properties of the obtained composite particles 7 are shown in Table 1.Production Example of Composite Particles 8Composite particles 8 were prepared in the same manner as in the preparation example of composite particles 1, except that the hydrophobicizing agent used was replaced with octamethylcyclotetrasiloxane in the hydrophobicizing step. The physical properties of the obtained composite particles 8 are shown in Table 1.Production Example of Composite Particles 9Composite particles 9 were obtained in the same manner as in the Production Example of Composite particles 1, except that hexamethyldisilazane was not added in the hydrophobization step. The physical properties of the obtained composite particles 9 are shown in Table 1.Production Example of Composite Particles 10Composite particles 10 were obtained in the same manner as in the preparation example of Composite particles 1, except that the amount of the colloidal silica dispersion liquid A in the item (2) of the 1st hydrolysis and polycondensation step described above was changed to 8.0 g. The physical properties of the obtained composite particles 10 are shown in Table 1.Production Example of Composite Particles 11Composite particles 11 were obtained in the same manner as in the Production Example of Composite particles 1, except that the amount of the colloidal silica dispersion liquid A in the above-described 1sthydrolysis and polycondensation step (2) was changed to 10.0 g. The physical properties of the obtained composite particles 11 are shown in Table 1.Production Example of Composite Particles 12Composite particles 12 were obtained in the same manner as in the preparation example of Composite particles 1, except that 7.0 g of an aqueous titanium oxide dispersion liquid (titanium oxide solid content: 40 mass %, particle diameter of 28 nm) was used instead of 5.0 g of the aqueous colloidal silica dispersion liquid A in the step (2) of the 1st hydrolysis and polycondensation step described above. The physical properties of the obtained composite particles 12 are shown in Table 1.Production Example of Composite Particles 13Composite particles 13 were obtained in the same manner as in the preparation example of composite particles 1, except that a colloidal silica dispersion liquid B (silica solid content: 40 mass %, particle diameter of 5 nm) was used instead of the colloidal silica dispersion aqueous liquid A, and the stirring temperature in the item (2) of the 1st hydrolysis and polycondensation step described above was changed to 28° C.The physical properties of the obtained composite particles 13 are shown in Table 1.Production Example of Composite Particles 14Composite particles 14 were obtained in the same manner as in the preparation example of Composite particles 1, except that a colloidal silica dispersion liquid C (silica solid content: 40 mass %, particle diameter of 70 nm) was used instead of the colloidal silica dispersion aqueous liquid A in the item (2) of the 1st hydrolysis and polycondensation step described above. The physical properties of the obtained composite particles 14 are shown in Table 1.Production Example of Composite Particles 15Composite particles 15 were obtained in the same manner as in the preparation example of composite particles 13 except that a colloidal silica dispersion liquid D (silica solid content: 40 mass %, particle diameter of 3 nm) was used instead of the colloidal silica dispersion aqueous liquid B in the item (2) of the 1st hydrolysis and polycondensation step described above. The physical properties of the obtained composite particles 15 are shown in Table 1.Production Example of Composite Particles 16Composite particles 16 were obtained in the same manner as in the preparation example of Composite particles 1, except that a colloidal silica dispersion liquid E (silica solid content: 40 mass %, particle diameter of 75 nm) was used instead of the colloidal silica dispersion aqueous liquid A in the step (2) of the 1st hydrolysis and polycondensation step described above. The physical properties of the obtained composite particles 16 are shown in Table 1.Production Example of Composite Particles 17Composite particles 17 were obtained in the same manner as in the production example of composite particles 16, except that the stirring temperature in the item (2) of the 1st hydrolysis and polycondensation step described above was changed to 28° C. The physical properties of the obtained composite particles 17 are shown in Table 1. Production Example of Composite Particles 18Composite particles 18 were obtained in the same manner as in the production example of composite particles 1, except that the stirring temperature in the item (2) of the 1st hydrolysis and polycondensation step described above was changed to 35° C. The physical properties of the obtained composite particles 18 are shown in Table 1. Production Example of Composite Particles 19Composite particles 19 were obtained in the same manner as in the Production Example of Composite particles 1, except that 2.0 g of 28% ammonia water and 15.0 g of tetraethoxysilane were added, the mixture was stirred at 30° C. for 2.5 hours, 5.0 g of the colloidal silica aqueous dispersion liquid A was added, and the mixture was further stirred for 0.5 hours to obtain a raw material solution in the step (2) of the 1st hydrolysis and polycondensation step described above. The physical properties of the obtained composite particles 19 are shown in Table 1.Production Example of Composite Particles 20Composite particles 20 were obtained in the same manner as in the preparation example of Composite particles 1, except that the amount of dimethyldimethoxysilane in the item (1) of the 1st hydrolysis and polycondensation step described above was changed to 3.2 g and the amount of tetraethoxysilane in the item (2) was changed to 24.0 g. The physical properties of the obtained composite particles 20 are shown in Table 1. Production Example of Composite Particles 21Composite particles 21 were obtained in the same manner as in the production example of composite particles 1, except that the amount of 28% ammonia water in the item (2) of the 1st hydrolysis and polycondensation step described above was changed to 1.8 g. The physical properties of the obtained composite particles 21 are shown in Table 1.Production Example of Composite Particles 22A 250 mL round-bottomed four-necked flask equipped with a stirring motor, a condenser, and a thermocouple was charged with 18.7 g of a colloidal silica dispersion liquid (silica solid content: 40 mass %, particle diameter: 30 nm), 125 mL of DI water, and 16.5 g (0.066 mol) of methacryloxypropyltrimethoxysilane. The temperature was raised to 65°C and the mixture was stirred at 120 U / min. The mixture was foamed for 30 minutes by flowing nitrogen gas through the mixture. After 3 hours, 0.16 g of a 2,2'-azobisisobutyronitrile radical initiator dissolved in 10 mL of ethanol was added to the mixture and the temperature was raised to 75 °C. Radical polymerization was carried out for 5 hours, and 3 ml of 1,1,1,3,3,3-hexamethyldisilazane was added to the mixture. The reaction was continued for an additional 3 hours. The final mixture was filtered through a 170 mesh screen to remove the coagulant material, and the dispersion liquid was dried in a Pyrex dish (registered trademark) at 120° C. overnight, thereby obtaining composite particles 22. The physical properties of the obtained composite particles 22 are shown in Table 1.Production Example of Composite Particles 23Composite particles 23 were obtained in the same manner as in the preparation example of Composite particles 1, except that 5.0 g of a Polyesterharzfeinteilchendispersionsflüssigkeit(Feinteilchenfeststoffgehalt: 30 mass %, particle diameter of 40 nm) was used instead of 5.0 g of the colloidal silica dispersion liquid A in the item (2) of the 1st hydrolysis and polycondensation step described above. The physical properties of the obtained composite particles 23 are shown in Table 1. Table 1 Table 1Composite Parts 1Organic silicon compound0,400,000,60Silica70600,300,12151,35HexamethyldisilazaneComposite Parts 2Organic silicon compound0,650,000,35Silica70600,300,12301,35HexamethyldisilazaneComposite Parts 3Organic silicon compound0,350,000,65Silica70600,300,12101,35HexamethyldisilazaneComposite Parts 4Organic silicon compound0,300,000,70Silica70600,300,1281,35HexamethyldisilazaneComposite Parts 5Organic silicon compound0,200,000,80Silica70600,300,1251,35HexamethyldisilazaneComposite Parts 6Organic silicon compound0,300,500,20Silica70600,300,12151,35HexamethyldisilazaneComposite Parts 7Organic silicon compound0,001,000,00Silica70600,300,12121,35HexamethyldisilazaneComposite Parts 8Organic silicon compound0,400,000,60Silica70600,300,12151,35OctamethylcyclotetrasiloxaneComposite Parts 9Organic silicon compound0,400,000,60Silica70600,300,12151,35no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no noComposite Parts 10Organic silicon compound0,400,000,60Silica70600,300,12231,60HexamethyldisilazaneComposite Parts 11Organic silicon compound0,400,000,60Silica70600,300,12261,70HexamethyldisilazaneComposite Parts 12Organic silicon compound0,400,000,60Titanium oxide150600,300,12281,50HexamethyldisilazaneComposite Parts 13Organic silicon compound0,400,000,60Silica70400,050,11151,35HexamethyldisilazaneComposite Parts 14Organic silicon compound0,400,000,60Silica70570,700,16151,35HexamethyldisilazaneComposite Parts 15Organic silicon compound0,400,000,60Silica70500,030,11151,35HexamethyldisilazaneComposite Parts 16Organic silicon compound0,400,000,60Silica70530,750,17151,35HexamethyldisilazaneComposite Parts 17Organic silicon compound0,400,000,60Silica70400,750,19151,35HexamethyldisilazaneComposite Parts 18Organic silicon compound0,400,000,60Silica701000,300,10151,35HexamethyldisilazaneComposite Parts 19Organic silicon compound0,400,000,60Silica70150,300,15151,35HexamethyldisilazaneComposite Parts 20Organic silicon compound0,800,000,20Silica70600,300,12321,35HexamethyldisilazaneComposite Parts 21Organic silicon compound0,400,000,60Silica70600,380,10151,35HexamethyldisilazaneComposite Parts 22Acrylic resin---Silica70600,300,12402,50no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no no noComposite Parts 23Organic silicon compound0,400,000,60Polyester20600,400,12131,35HexamethyldisilazanePreparation Example of Silica Fine Particles 1Oxygen gas and hydrogen gas were supplied to form a flame, and silicon tetrachloride, which was a raw material, was added for gasification, thereby obtaining silica fine particles. The obtained silica fine particles were transferred to an electric furnace, sprayed into a thin layer, and sintered by a heat treatment at 900° C. Thereafter, the resultant was subjected to surface treatment with hexamethyldisilazane as a hydrophobicizing agent, whereby silica fine particles 1 were obtained. Physical properties of the obtained silica fine particles 1 are shown in Table 2. Production Examples of Silica Fine Particles 2 to 4The silica fine particles 2 to 4 were obtained by adjusting the addition amount of silicon tetrachloride, the supply amount of oxygen gas, the supply amount of hydrogen gas, the concentration of the silica fine particles, the retention time, the temperature and time for sintering, and the kind of the surface treatment agent. Physical properties of the obtained silica fine particles 2 to 4 are shown in Table 2.Production Example of Silica Fine Particles 5Silica fine particles 5 were prepared in the same manner as in the preparation example of silica fine particles 1 except that the used hydrophobicizing agent was replaced with chloromethylsilane. Physical properties of the obtained silica fine particles 5 are shown in Table 2.Production Example of Silica Fine Particles 6Silica fine particles 6 were obtained in the same manner as in the preparation example of silica fine particles 1 except that the used hydrophobicizing agent was not used. Physical properties of the obtained silica fine particles 6 are shown in Table 2. Table 2 Table 2Silica Fine Particles 10,10HexamethyldisilazaneSilica Fine Particles 20,12HexamethyldisilazaneSilica Fine Particles 30,35HexamethyldisilazaneSilica Fine Particles 40,02HexamethyldisilazaneSilica Fine Particles 50,10ChlorotrimethylsilaneSilica Fine Particles 60,10None of them wereProduction Example of Polyester Resin A1polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane: 76.9 parts (0.167 mol)Terephthalic acid (TPA): 25.0 parts (0.145 mole)Adipic acid: 8.0 parts (0.054 mol)titanium tetrabutoxide: 0.5 partsThe above-described materials were placed in a 4 liter four-necked glass flask, and a thermometer, a stirring bar, a condenser and a nitrogen inlet tube were attached to the flask and placed in a heating jacket. Then, the inside of the flask was substituted with nitrogen gas and heated gradually with stirring, and the mixture was allowed to react for 4 hours with stirring at a temperature of 200°C (first reaction step). Thereafter, 1.2 parts (0.006 mol) of trimellitic anhydride (TMA) was added, and the mixture was allowed to react at 180°C for 1 hour (second reaction step), thereby obtaining a polyester resin A1 serving as a binder resin component. The acid number of the polyester resin A1 was 5 mgKOH / g.Production Example of Polyester Resin A2polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane: 71.3 parts (0.155 mole)Terephthalic acid: 24.1 parts (0.145 mole)titanium tetrabutoxide: 0.6 partsThe above-described materials were placed in a 4-liter four-necked glass flask, and a thermometer, a stirring bar, a condenser and a nitrogen inlet tube were attached to the flask and placed in a heating jacket. Then, the inside of the flask was substituted with nitrogen gas and heated gradually with stirring, and the mixture was allowed to react for 2 hours with stirring at a temperature of 200°C. Thereafter, 5.8 parts (0.030 mol %) of trimellitic anhydride was added, and the mixture was allowed to react at 180° C. for 10 hours, thereby obtaining a polyester resin A2. The acid number of the polyester resin A2 was 10 mgKOH / g.Production Example of Toner Particles 1polyester resin A1: 70.0 partspolyester resin A2: 30.0 partsFischer-Tropsch wax (peak temperature of maximum endothermic peak: 78°C): 5.0 partsC. I. Pigment Blue 15:3:5.0 parts3,5-Di-t-butylsalicylic acid aluminum compound: 0.1 partThe raw materials in the above-described formulation were mixed at a rotation speed of 20 sec -1 for a rotation time of 5 minutes with a Henschel mixer (Model FM-75 manufactured by NIPPON COKE & ENGINEERING CO., LTD.), and kneaded with a twin-screw kneader (Model PCM-30 manufactured by IKEGAI CO., LTD.) at a temperature of 125° C. and a rotation speed of 300 U / min. The obtained kneaded material was cooled and roughly crushed to a diameter of 1 mm or less with a hammer mill to obtain a roughly crushed material. The coarse crushed material thus obtained was finely pulverized by a mechanical crusher (T-250 manufactured by FREUND-TURBO CORPORATION). Subsequently, the material was classified with a rotary classifier (200TSP manufactured by Hosokawa Micron Corporation), whereby toner particles 1 were obtained. The rotary separator was operated at a classification rotor rotational speed of 50.0 s -1. The obtained toner particles 1 had a weight average molecular weight (D4) of 5.9 μm.Production Example of Toner 1Toner particles 1: 100 partsComposite particles 1: 2.0 partssilica fine particles 1: 2.0 partsThe above-described materials were mixed at a rotation speed of 30 sec -1 for a rotation time of 10 min with a Henschel mixer Model FM-10c (manufactured by Mitsui Mike Kakoki Co., Ltd.), whereby a toner 1 was obtained.Production Examples of Toners 2 to 35Toners 2 to 35 were produced in the same manner as described above, except that the types and the addition amounts of the composite particles and the silica fine particles in the production example of the toner 1 were changed as listed in Table 3. Physical properties of toners 2 to 35 are shown in Table 3. Table 3 <row><cell>Toner 1< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 2< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 2< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 3< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 3< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 4< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 4< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 5< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 5< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 6< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 6< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 7< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 7< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 8< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 8< / cell><cell>2,0< / cell><cell>Silica Fine Particles 5< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 9< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 8< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 10< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 9< / cell><cell>2,0< / cell><cell>Silica Fine Particles 6< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 11< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 10< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 12< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 11< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 13< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 12< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 14< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>0,3< / cell><cell>Silica Fine Particles 1< / cell><cell>3,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 15< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>3,0< / cell><cell>Silica Fine Particles 1< / cell><cell>0,3< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 16< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>0,1< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 17< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>0,1< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 18< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>1,0< / cell><cell>Silica Fine Particles 1< / cell><cell>20,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 19< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>20,0< / cell><cell>Silica Fine Particles 1< / cell><cell>1,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 20< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>0,08< / cell><cell>Silica Fine Particles 1< / cell><cell>0,08< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 21< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>25,0< / cell><cell>Silica Fine Particles 1< / cell><cell>25,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 22< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 13< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,03< / cell>< / row><row><cell>Toner 23< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 14< / cell><cell>2,0< / cell><cell>Silica Fine Particles 2< / cell><cell>2,0< / cell><cell>1,3< / cell><cell>0,25< / cell>< / row><row><cell>Toner 24< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 15< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,1< / cell><cell>0,02< / cell>< / row><row><cell>Toner 25< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 16< / cell><cell>2,0< / cell><cell>Silica Fine Particles 2< / cell><cell>2,0< / cell><cell>1,4< / cell><cell>0,29< / cell>< / row><row><cell>Toner 26< / cell><cell>Toner Particles 1< / cell><cell>Composite particles 17< / cell><cell>2,0< / cell><cell>Silica Fine Particles 2< / cell><cell>2,0< / cell><cell>1,6< / cell><cell>0,37< / cell>< / row><row><cell>Toner 27< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 18< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,0< / cell><cell>0,00< / cell>< / row><row><cell>Toner 28< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 19< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,5< / cell><cell>0,26< / cell>< / row><row><cell>Toner 29< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 20< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 30< / cell><cell>Toner Particles 1< / cell><cell>Composite particles 21< / cell><cell>2,0< / cell><cell>Silica Fine Particles 3< / cell><cell>2,0< / cell><cell>0,3< / cell><cell>0,03< / cell>< / row><row><cell>Toner 31< / cell><cell>Toner Particles 1< / cell><cell>Composite particles 21< / cell><cell>2,0< / cell><cell>Silica Fine Particles 4< / cell><cell>2,0< / cell><cell>5,0< / cell><cell>0,60< / cell>< / row><row><cell>Toner 32< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 22< / cell><cell>2,0< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,12< / cell>< / row><row><cell>Toner 33< / cell><cell>Toner Particles 1< / cell><cell>Composite particles 23< / cell><cell>2,0< / cell><cell>Silica Particles 1< / cell><cell>2,0< / cell><cell>1,2< / cell><cell>0,16< / cell>< / row><row><cell>Toner 34< / cell><cell>Toner Particles 1< / cell><cell>Composite Particles 1< / cell><cell>2,0< / cell><cell>-< / cell><cell>-< / cell><cell>-< / cell><cell>-< / cell>< / row><row><cell>Toner 35< / cell><cell>Toner Particles 1< / cell><cell>-< / cell><cell>-< / cell><cell>Silica Fine Particles 1< / cell><cell>2,0< / cell><cell>-< / cell><cell>-< / cell>< / row><head xml:id="_12c2da1017">Production Example of Support 1< / head><p xml:id="_12c2da1018"><list xml:id="_12c2da1019" type="bulleted"><item>magnetite 1 having a number average particle diameter of 0.30 μm (magnetization strength of 65 Am <hi rend="superscript">2< / hi> / kg in a magnetic field of 1000 / 4π (kA / m))< / item><item>magnetite 2 having a number average particle diameter of 0.50 μm (magnetization strength of 65 Am <hi rend="superscript">2< / hi> / kg in a magnetic field of 1000 / 4π (kA / m))< / item>< / list><p xml:id="_12c2da1024" n="0145">4,0 Parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added to 100 parts of each of the materials described above, the mixture was mixed and stirred in a container at 100° C. or higher at high speed to treat each of the fine particles.<list xml:id="_12c2da1025" type="bulleted"><item>phenol: 10 mass %< / item><item>formaldehyde solution: 6% by mass (40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water)< / item><item>Magnetite 1 treated with the above-described silane compound: 58% by mass< / item><item>Magnetite 2 treated with the above-described silane compound: 26 mass%< / item>< / list><p xml:id="_12c2da1030" n="0146">100 Parts of the above-described materials, 5 parts of an aqueous solution containing 28% by mass of ammonia and 20 parts of water were placed in a flask, heated to 85° C., and maintained at this temperature for 30 minutes while stirring and mixing, and subjected to polymerization reaction for 3 hours to cure a resulting phenolic resin. Thereafter, the cured phenolic resin was cooled to 30°C, water was further added, the supernatant was removed, the precipitate was washed with water and air-dried. Subsequently, the resultant was dried at a temperature of 60° C. under reduced pressure (5 mmHg or less), whereby a spherical magnetic material-dispersed support 1 was obtained. The 50% particle diameter (D50) on a volume basis thereof was 34.2 μm.<head xml:id="_12c2da1031">Production Example of Two-Component Developer 1< / head><p xml:id="_12c2da1032" n="0147">8,0 Parts of the toner 1 was added to 92.0 parts of the carrier 1, and the mixture was mixed with a V mixer (V-20 manufactured by SEISHIN ENTERPRISE Co., Ltd.), whereby a two-component developer 1 was obtained.<head xml:id="_12c2da1033">Production Examples of Two-Component Developer 2 to 35< / head><p xml:id="_12c2da1034" n="0148">Two-component developers 2 to 35 were prepared in the same manner as described above except that the toner was changed as shown in Table 4 as in the preparation example of the two-component developer 1. Table 4<title desc="title">Table 4Two-component developer 1Toner 1Support 1Two-component developer 2Toner 2Support 1Two-component developer 3Toner 3Support 1Two-component developer 4Toner 4Support 1Two-component developer 5Toner 5Support 1Two-component developer 6Toner 6Support 1Two-component developer 7Toner 7Support 1Two-component developer 8Toner 8Support 1Two-component developer 9Toner 9Support 1Two-component Developer 10Toner 10Support 1Two-component developer 11Toner 11Support 1Two-component developer 12Toner 12Support 1Two-component developer 13Toner 13Support 1Two-component developer 14Toner 14Support 1Two-component developer 15Toner 15Support 1Two-component developer 16Toner 16Support 1Two-component developer 17Toner 17Support 1Two-component developer 18Toner 18Support 1Two-component developer 19Toner 19Support 1Two-component developer 20Toner 20Support 1Two-component developer 21Toner 21Support 1Two-component developer 22Toner 22Support 1Two-component developer 23Toner 23Support 1Two-component developer 24Toner 24Support 1Two-component developer 25Toner 25Support 1Two-component developer 26Toner 26Support 1Two-component developer 27Toner 27Support 1Two-component developer 28Toner 28Support 1Two-component developer 29Toner 29Support 1Two-component developer 30Toner 30Support 1Two-component developer 31Toner 31Support 1Two-component developer 32Toner 32Support 1Two-component developer 33Toner 33Support 1Two-component developer 34Toner 34Support 1Two-component developer 35Toner 35Support 1Examples 1 to 26 and Comparative Examples 1 to 9Method for Toner EvaluationThe above-obtained Developers 1 to 35 were evaluated as follows.In the evaluation, a color copying machine imagePRESS C850 (manufactured by CANON INC.) or a modified machine thereof was used as the image forming machine.Each developer was placed in a cyan color developing device of an image forming apparatus, and the dot reproducibility before and after a paper feeding endurance test was subjected.Dot reproducibility was evaluated by conducting a paper feed endurance test under a printing environment (hereinafter referred to as "N / L environment") having a temperature of 23° C. and a relative humidity of 5%, and producing 10000 sheets of images with a test batch having an aspect ratio of 5%. Conditions for the paper feed endurance test for evaluation of dot reproducibility:Paper: recycled copying paper, GF-R100W (A4, basis weight 67 g / m 2, sold by Canon Marketing Japan Inc.)Image forming speed: A4 size, full color, 85 sheets / minDevelopment conditions: The modification was made so that the development contrast could be set to any value and the automatic correction was not controlled by the main apparatus.Dot reproducibilityThe dot reproducibility before and after the paper feeding endurance test was evaluated as follows. Halftone images (30h) were produced and evaluated according to the following criteria. Further, the 30h image denotes a half tone image in which the 256 gradations are expressed in hexadecimal values, 00h is defined as solid white (non-image), and FFh is defined as solid image (frame). The areas of 1000 points of the image were measured with a digital microscope VHX-500 (wide angle zoom lens VH-Z100 manufactured by KEYENCE CORPORATION). The number average (S) of the dot areas and the standard deviation (σ) of the dot areas were calculated, and the index of the dot reproducibility was determined from the following equation.The evaluation of dot reproducibility was made on the basis of the dot reproducibility index of the halftone image. The dot reproducibility is excellent when the value of the dot reproducibility index decreases. A rank of G or higher was determined to indicate that the effects of the present disclosure have been achieved. The evaluation results are shown in Table 5.Criteria for EvaluationA: The dot reproducibility was less than 1.0.B: The dot reproducibility was 1.0 or more and less than 2.0.C: The dot reproducibility was 2.0 or more and less than 3.0.D: The dot reproducibility was 3.0 or more and less than 4.0.E: The dot reproducibility was 4.0 or more and less than 5.0.F: The dot reproducibility was 5.0 or more and less than 6.0.G: The dot reproducibility was 6.0 or more and less than 7.0.H: The dot reproducibility was 7.0 or more.Table 5 Table 5Example 1Two-component developer 10,8A. A0,9A. AExample 2Two-component developer 20,8A. A1,4B. BExample 3Two-component developer 30,8A. A1,5B. BExample 4Two-component developer 40,8A. A2,1C. CExample 5Two-component developer 50,9A. A3,3D. DExample 6Two-component developer 60,8A. A1,1B. BExample 7Two-component developer 70,8A. A1,2B. BExample 8Two-component developer 81,7B. B1,9B. BExample 9Two-component developer 92,3C. C2,4C. CExample 10Two-component Developer 102,5C. C2,6C. CExample 11Two-component developer 111,7B. B2,8C. CExample 12Two-component developer 121,8B. B3,2D. DExample 13Two-component developer 132,8C. C2,9C. CExample 14Two-component developer 142,7C. C2,9C. CExample 15Two-component developer 153,5D. D3,5D. DExample 16Two-component developer 163,2D. D3,5D. DExample 17Two-component developer 174,2E. E4,2E. EExample 18Two-component developer 184,2E. E4,6E. EExample 19Two-component developer 195,3F. F5,3F. FExample 20Two-component developer 206,5G.6,8G.Example 21Two-component developer 215,7F. F5,9F. FExample 22Two-component developer 224,5E. E4,7E. EExample 23Two-component developer 234,7E. E4,7E. EExample 24Two-component developer 245,1F. F5,3F. FExample 25Two-component developer 255,2F. F5,3F. FExample 26Two-component developer 266,5G.6,7G.Comparative Example 1Two-component developer 277,1H. H. The reaction temperature is high7,2H. H. The reaction temperature is highComparative Example 2Two-component developer 284,8E. E7,8H. H. The reaction temperature is highComparative Example 3Two-component developer 291,2B. B8,0H. H. The reaction temperature is highComparative Example 4Two-component developer 307,5H. H. The reaction temperature is high7,8H. H. The reaction temperature is highComparative Example 5Two-component developer 318,1H. H. The reaction temperature is high8,2H. H. The reaction temperature is highComparative Example 6Two-component developer 322,1C. C7,2H. H. The reaction temperature is highComparative Example 7Two-component developer 337,2H. H. The reaction temperature is high8,5H. H. The reaction temperature is highComparative Example 8Two-component developer 348,9H. H. The reaction temperature is high9,2H. H. The reaction temperature is highComparative Example 9Two-component developer 357,3H. H. The reaction temperature is high9,2H. H. The reaction temperature is highAlthough the present disclosure has been described with reference to exemplary embodiments, the disclosure is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be construed as broadly as possible to include all such modifications and equivalent structures and functions.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Patent Literature citedJP 5-72801

[0003] JP 8-220874

[0003] JP 5982003 [0004, 0006]

Claims

A toner comprising: a toner particle; a composite particle present on a surface of the toner particle; and a spherical silica fine particle, wherein the composite particle includes a fine particle A containing, as a binder component, an organic silicon compound having a siloxane bond and a fine particle B being an inorganic fine particle, wherein the fine particle B is present on a surface of the composite particle in a state in which a part of the fine particle B is embedded in a surface of the fine particle A, wherein Da is a number-average particle diameter of the composite particle and Db is a number-average particle diameter of the spherical silica fine particle, wherein Db is 0.03 μm or more and 0.30 μm or less, and 0.4 ≤ Da / Db ≤ 1.8 is satisfied, and wherein Pa is a proportion of a silicon atom represented by Si a in a structure represented by a unit (a), Pb is a proportion of a silicon atom represented by Si b in a structure represented by a unit (b), Pc is a proportion of a silicon atom represented by Si c in a structure represented by a unit (c), based on all silicon atoms contained in the organic silicon compound of the fine particle A, and Pa, Pb and Pc satisfy the expressions (1) to (3), Pa + Pb + Pc ≥ 0.80 Pb + Pc ≥ 0.30 Pa ≤ 0.70 ( R 1 and R 2 represent an alkyl group having 1 or more and 6 or less carbon atoms), wherein an average value of the embedding ratios of the fine particle B to the fine particle A in the composite particle represented by the following equation is 30% or more and 90% or less, embedding ratio a%0020̈ cases (%) of fine particles B to fine particles A=(depth of embedding of fine particles B in fine particles B in fine particles A / diameter of fine particles B)×100. The toner according to claim 1, wherein Dc is an average height of portions of the fine particle B protruding from the fine particle A, and 0.03 ≤ Dc / Db ≤ 0.30 is satisfied.The toner according to claim 1 or 2, wherein A D is a number-average primary particle diameter of a fine particle A, B D is a number-average primary particle diameter of the fine particle B, and a ratio B D / A is D0,05 or more and 0.70 or less.The toner according to any one of claims 1 to 3, wherein the fine particle B has a Young's modulus of 50 GPa or more.The toner according to any one of claims 1 to 4, wherein a content of the composite particle is 0.1 parts by mass or more and 20.0 parts by mass or less, based on 100 parts by mass of the toner particle.The toner according to any one of claims 1 to 5, wherein a content of the spherical silica fine particle is 0.1 parts by mass or more and 20.0 parts by mass or less, based on 100 parts by mass of the toner particle.The toner according to any one of claims 1 to 6, wherein a ratio (content of composite particles with respect to 100 parts by mass of toner particles) / (content of spherical silica fine particles with respect to 100 parts by mass of toner particles) is 0.2 or more and 5.0 or less.The toner according to any one of claims 1 to 7, wherein the fine particle B is silica.The toner according to any one of claims 1 to 8, wherein the composite particle has a true specific gravity of 1.00 g / cm 3 or more and 1.60 g / cm 3 or less.The toner according to any one of claims 1 to 9, wherein both the composite particle and the spherical silica fine particle are subjected to surface treatment with the same compound selected from the group consisting of an alkyl silazane compound, an alkylalkoxysilane compound, a chlorosilane compound, a siloxane compound, and silicone oil.The toner according to any one of claims 1 to 10, wherein Pa, Pb and Pc satisfy the expressions (I), (II) and (III), 0.30 ≤ Pa / ( Pa + Pb + Pc ) ≤ 0.70 0 ≤ Pb / ( Pa + Pb + Pc ) ≤ 0.50 0,20 ≤ Pc / ( Pa + Pb + Pc ) ≤ 0.70 The toner according to any one of claims 1 to 11, wherein the composite particle has a Young's modulus of 10 GPa or more and 30 GPa or less.