External additive for toner and toner

Abstract

To provide an external additive toner in which toner charging quickly builds up even when an image is output in a high humidity environment, has charge stability, and provides an image with a reduced density variation and hue variation.SOLUTION: An external additive for toner includes an organic silicon polymer having a siloxane bond. In X-ray photoelectron spectrometry of the external additive for toner, when the concentration of silicon atoms is defined as dSi, the concentration of oxygen atoms as dO, and the concentration of carbon atoms as dC (total 100 atom%), the concentration of carbon atoms coupled to silicon is 30-60 atom%, the amount of a silanol group measured in titration using KOH is 0.025-0.800 mmol / g, and when the total number of silicon atoms is defined as 1.00, the concentration of silicon atoms indicated by Sia in the following (a) as Pa, the concentration of silicon atoms indicated by Sib in the following (b) as Pb, and the concentration of silicon atoms indicated by Sic in the following (c) as Pc, the following formulas (1)-(2) are satisfied. (1) (Pa)+(Pb)+(Pc)≥0.80, and (2) (Pb)+(Pc)≥0.30. (R1 and R2 are each independently an alkyl group having 1-6 carbon atoms.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an external toner additive and a toner. [Background technology]

[0002] In recent years, electrophotographic full-color copiers have become widespread and are beginning to be applied to the printing market, where there is a growing demand for high speed, high image quality, and high stability. To achieve high and stable image quality, it is necessary to stabilize the charging characteristics of the toner. In order to stabilize the charging characteristics of the toner, various external additives have been investigated. Conventionally, silica has been widely known as an external additive used in toner. Generally, examples have been reported in which silica obtained by a dry or wet method (sol-gel method) has been subjected to a surface treatment to enhance hydrophobicity. For example, Patent Document 1 discloses an example in which highly hydrophobic spherical sol-gel silica microparticles are added to toner particles (toner base particles) to improve the charging stability of the toner. Furthermore, Patent Document 2 discloses an example in which polyalkylsilsesquioxane fine particles are added to toner base particles to improve the fluidity and charging stability of the toner. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-99582 [Patent Document 2] Patent No. 6116711 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in a high humidity environment, the initial chargeability of the toner rises slowly, which can result in significant fluctuations in density or color of images when images are continuously output. The object of the present disclosure is to provide an external toner additive and a toner that solve the above-mentioned problems. Specifically, even when an image is printed in a high-humidity environment, the toner quickly builds up charge, has charge stability, and can produce images with reduced density and color variations. [Means for solving the problem]

[0005] The present disclosure provides an external toner additive comprising an organosilicon polymer having a siloxane bond, In the external toner additive, when measured by X-ray photoelectron spectroscopy, the atomic concentration of silicon atoms is dSi, the atomic concentration of oxygen atoms is dO, and the atomic concentration of carbon atoms is dC, and the sum of these is taken as 100 atomic %, the atomic concentration of carbon atoms bonded to silicon atoms is 30 atomic % or more and 60 atomic % or less; the external toner additive has a silanol group amount of 0.025 mmol / g or more and 0.800 mmol / g or less, as measured by a titration method using KOH; Regarding the silicon atoms contained in the organosilicon polymer, the total number of silicon atoms is set to 1.00, and the Si in the structure represented by the following unit (a) is a The ratio of silicon atoms represented by Pa is the ratio of Si in the structure represented by the following unit (b). b The ratio of silicon atoms represented by Pb and Si in the structure represented by the following unit (c) c The external toner additive is characterized in that, when the ratio of silicon atoms represented by the formula (1) is defined as Pc, Pa, Pb and Pc satisfy the following formulae (1) and (2): (1)(Pa)+(Pb)+(Pc)≧0.80 (2)(Pb)+(Pc)≧0.30

[0006] [ka] (R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms.) The present disclosure also provides a toner having toner particles and an external additive, wherein the external additive has the above-described configuration. [Effects of the Invention]

[0007] According to the present disclosure, even when an image is output in a high-humidity environment, the toner charge builds up quickly, and an image with stable charge and reduced density and color variations can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0008] In the present disclosure, unless otherwise specified, the expressions "xx or more and xx or less" and "xx to xx" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints.

[0009] The present inventors believe that the mechanism by which the effects of the present disclosure are realized is as follows.

[0010] Silica particles and polyalkylsilsesquioxane particles, which have traditionally been used as external toner additives, are particles primarily composed of siloxane bonds (Si-O-Si). Silanol groups exist at the ends of silica particles and polyalkylsilsesquioxane particles, resulting in the presence of unreacted silanol groups on the particle surface and inside. Because silanol groups readily adsorb moisture, the charge of toner particles decreases in high-humidity environments.

[0011] To address this issue, the remaining silanol groups are subjected to a coupling reaction with a silane compound or the like to be trimethylsilylated (surface treatment), thereby improving the chargeability in high humidity environments. On the other hand, the charge buildup of toner is greatly influenced by charging due to ion migration of hydroxyl groups, and it has been found that external additives with few silanol groups that have been subjected to the above-mentioned surface treatment slow down the charge buildup.

[0012] After extensive research, the inventors discovered that the above problems could be solved by optimizing the atomic concentration of carbon atoms bonded to silicon atoms and the amount of silanol groups in the organosilicon polymer, leading to the present disclosure.

[0013] [Toner additives] The present disclosure provides an external toner additive comprising an organosilicon polymer having a siloxane bond, In the external toner additive, when measured by X-ray photoelectron spectroscopy, the atomic concentration of silicon atoms is dSi, the atomic concentration of oxygen atoms is dO, and the atomic concentration of carbon atoms is dC, and the sum of these is taken as 100 atomic %, the atomic concentration of carbon atoms bonded to silicon atoms is 30 atomic % or more and 60 atomic % or less; the external toner additive has a silanol group amount of 0.025 mmol / g or more and 0.800 mmol / g or less, as measured by a titration method using KOH; Regarding the silicon atoms contained in the organosilicon polymer, the total number of silicon atoms is set to 1.00, and the Si in the structure represented by the following unit (a) is a The ratio of silicon atoms represented by Pa is the ratio of Si in the structure represented by the following unit (b). b The ratio of silicon atoms represented by Pb and Si in the structure represented by the following unit (c) c When the proportion of silicon atoms represented by the following formula (1) is defined as Pc, the Pa, Pb, and Pc satisfy the following formulas (1) and (2). (1)(Pa)+(Pb)+(Pc)≧0.80 (2)(Pb)+(Pc)≧0.30

[0014] [ka] (R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms.)

[0015] First, in the external toner additive of the present disclosure, when the atomic concentration of silicon atoms is dSi, the atomic concentration of oxygen atoms is dO, and the atomic concentration of carbon atoms is dC, and the sum of these is taken as 100 atomic %, the atomic concentration of carbon atoms bonded to silicon atoms is 30 atomic % or more and 60 atomic % or less in X-ray photoelectron spectroscopy measurement.

[0016] Within the above range, the toner's chargeability rises smoothly and its durability is excellent, resulting in improved image density and color stability. If the atomic concentration of carbon atoms is less than 30 atomic %, the hydrophobicity is insufficient, slowing the charge rise speed in high-humidity environments. If the atomic concentration of carbon atoms is more than 60 atomic %, the mechanical strength of the particles decreases, causing external additives to be crushed and reducing the charge stability of the toner.

[0017] The atomic concentration of carbon atoms in the external toner additive can be controlled by the mixing ratio of the alkoxysilane having the above structure, and the type and amount of surface treatment agent added. For example, to reduce the atomic concentration of carbon atoms, the mixing ratio of the alkoxysilane having the above structure (a) can be increased, the mixing ratio of the alkoxysilane having the above structures (b) to (c) can be decreased, or the amount of surface treatment agent added can be decreased. To increase the atomic concentration of carbon atoms, the mixing ratio of the alkoxysilane having the above structure (a) can be decreased, the mixing ratio of the alkoxysilane having the above structures (b) to (c) can be increased, or the amount of surface treatment agent added can be increased. The atomic concentration of carbon atoms in the external toner additive is more preferably 30 atomic % or more and 40 atomic % or less.

[0018] Next, the external toner additive of the present disclosure has a silanol group content of 0.025 mmol / g or more and 0.800 mmol / g or less, as measured by titration using KOH. By ensuring that the silanol group content is within this range, the charge build-up speed of the toner can be increased in a high-humidity environment. This improves initial charge stability and suppresses fluctuations in image density and color.

[0019] The amount of silanol groups in the external toner additive can be controlled by the mixing ratio of the alkoxysilane having the above structure, the temperature and time of the hydrolysis and condensation steps, the type and amount of surface treatment agent, and the treatment conditions. For example, to increase the amount of silanol groups, methods include increasing the mixing ratio of the alkoxysilane having the above structure (a), decreasing the mixing ratio of the alkoxysilane having the above structures (b) to (c), increasing the temperature of the hydrolysis and condensation steps, and lengthening the time of the hydrolysis and condensation steps. To decrease the amount of silanol groups, methods include decreasing the mixing ratio of the alkoxysilane having the above structure (a), increasing the mixing ratio of the alkoxysilane having the above structures (b) to (c), decreasing the temperature of the hydrolysis and condensation steps, and shortening the time of the hydrolysis and condensation steps.

[0020] Furthermore, with respect to the silicon atoms contained in the organosilicon polymer contained in the external toner additive of the present disclosure, the total number of silicon atoms is set to 1.00, and the number of Si atoms in the structure represented by the above unit (a) is a The ratio of silicon atoms represented by Pa is the ratio of Si in the structure represented by the above unit (b). b The ratio of silicon atoms represented by Pb and Si in the structure represented by the above unit (c) c When the proportion of silicon atoms represented by the formula (1) is defined as Pc, the Pa, the Pb, and the Pc satisfy the following formulas (1) and (2). (1)(Pa)+(Pb)+(Pc)≧0.80 (2)(Pb)+(Pc)≧0.30

[0021] Within the above range, the external additive itself is less likely to be destroyed when the toner is subjected to stress from components such as the carrier, and furthermore, due to its moderate flexibility, the external additive can be prevented from being embedded in the toner particle surface. Therefore, the toner surface condition is less likely to change, and changes in the toner's chargeability and adhesive force can be further suppressed. The content ratios of the above units (a), (b), and (c) in the external additive can be controlled by the amount of alkoxysilane having the above structure added.

[0022] <Method of manufacturing external toner additives> The method for producing the external toner additive of the present disclosure is not particularly limited, but it is preferable to form particles through hydrolysis and condensation polymerization of a silicon compound (silane monomer) by a sol-gel method. Specifically, it is preferable to hydrolyze and condense a mixture of a bifunctional silane having two siloxane bonds and a tetrafunctional silane having four siloxane bonds, and then react the mixture with colloidal silica or the like to form composite particles. Silane monomers such as bifunctional silanes and tetrafunctional silanes, and composite particles, will be described later. The proportion of the bifunctional silane is preferably 30 mol% to 70 mol%, more preferably 40 mol% to 60 mol%. The proportion of the tetrafunctional silane is preferably 30 mol% to 80 mol%, more preferably 40 mol% to 70 mol%.

[0023] The external toner additive of the present disclosure is a particle containing an organosilicon polymer having a siloxane bond.

[0024] There are no particular limitations on the method for producing organosilicon polymers. For example, a silane compound can be added dropwise to water, hydrolyzed and condensed in the presence of a catalyst, and the resulting suspension can be filtered and dried. The particle size can be controlled by the type of catalyst, the compounding ratio, the reaction initiation temperature, the dropwise addition time, etc. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include, but are not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0025] The external toner additive containing the organosilicon polymer is preferably produced by the following method.

[0026] Specifically, the method preferably includes a first step of obtaining a hydrolyzate of a silicon compound, a second step of mixing the hydrolyzate with an alkaline aqueous medium to polycondense the hydrolyzate, and a third step of mixing the polycondensation reaction product with an aqueous solution to form particles. In some cases, a hydrophobizing agent may also be added. Furthermore, in the second step, inorganic fine particles such as colloidal silica or resin fine particles may be used. As will be described in detail later, these fine particles become fine particles B in the composite particles.

[0027] In the first step, a silicon compound is contacted with a catalyst by stirring, mixing, or the like in an aqueous solution in which an acidic or alkaline substance serving as a catalyst is dissolved in water. Known catalysts can be suitably used. Specific examples of acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0028] The amount of catalyst used may be adjusted appropriately depending on the type of silicon compound and catalyst. Preferably, the amount of catalyst used is 1×10 -3 The amount is selected from the range of 1 part by mass or more and 1 part by mass or less.

[0029] The amount of catalyst used is 1×10 -3 If the amount of catalyst used is 1 part by mass or more, the reaction proceeds sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles will be low, making hydrolysis easier. The amount of water used is preferably 2 to 15 moles per mole of silicon compound. If the amount of water is 2 moles or more, the hydrolysis reaction will proceed sufficiently, and if it is 15 moles or less, productivity will be improved.

[0030] The reaction temperature is not particularly limited and may be carried out at room temperature or under heating, but it is preferable to carry out the reaction at a temperature maintained at 10 to 60° C., as this allows a hydrolysate to be obtained in a short time and prevents a partial condensation reaction of the produced hydrolysate. The reaction time is not particularly limited and may be appropriately selected taking into consideration the reactivity of the silicon compound used, the composition of the reaction liquid obtained by mixing the silicon compound, acid, and water, and productivity.

[0031] In the second step of the method for producing silicon polymer particles, the raw material solution obtained in the first step is mixed with an alkaline aqueous medium to polycondense the particle precursor, thereby obtaining a polycondensation reaction solution. Here, the alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0032] The alkaline component used in the alkaline aqueous medium is one whose aqueous solution is basic and acts as a neutralizer for the catalyst used in step 1 and as a catalyst for the polycondensation reaction in step 2. Examples of such alkaline components include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine.

[0033] The amount of the alkali component used is an amount that neutralizes the acid and effectively acts as a catalyst for the polycondensation reaction. For example, when ammonia is used as the alkali component, the amount is usually selected in the range of 0.01 parts by mass or more and 12.5 parts by mass or less per 100 parts by mass of the mixture of water and the organic solvent.

[0034] In the second step, in order to prepare an alkaline aqueous medium, an organic solvent may be used in addition to the alkaline component and water. The organic solvent is not particularly limited as long as it is compatible with water, but an organic solvent that dissolves 10 g or more of water per 100 g at room temperature and normal pressure is preferred.

[0035] Specific examples include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethers such as ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0036] Among the organic solvents listed above, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, etc. are preferred. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reactions, it is more preferred to select as the organic solvent the same alcohol as the alcohol produced by elimination.

[0037] In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. Water (tap water, pure water, etc.) is preferably used as the aqueous solution, but components compatible with water, such as salts, acids, alkalis, organic solvents, surfactants, and water-soluble polymers, may also be added to the water. The temperatures of the polycondensation reaction liquid and the aqueous solution when mixed are not particularly limited, and are preferably selected in the range of 5 to 70°C, taking into consideration the composition, productivity, etc.

[0038] The method for recovering particles can be any known method without any particular limitation. For example, a method of scooping floating powder or a filtration method can be mentioned, but filtration is preferred because of its simple operation. The filtration method is not particularly limited, and known devices such as vacuum filtration, centrifugal filtration, and pressure filtration can be selected. The filter paper, filter, filter cloth, etc. used for filtration are not particularly limited as long as they are industrially available, and can be appropriately selected depending on the device used.

[0039] The monomer to be used can be appropriately selected depending on its compatibility with the solvent and catalyst, its hydrolysis property, etc. Examples of the tetrafunctional silane monomer having the above structure (a) include tetramethoxysilane, tetraethoxysilane, and tetraisocyanatesilane, with tetraethoxysilane being preferred.

[0040] Examples of trifunctional silane monomers having the structure (b) include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethoxyhydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, Examples of such silane include ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane. Of these, methyltrimethoxysilane is preferred.

[0041] Examples of bifunctional silane monomers having the above structure (c) include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and diethyldimethoxysilane, and among these, dimethyldimethoxysilane is preferred.

[0042] <Preferable properties and aspects of external toner additives> The number-average diameter of the primary particles of the external toner additive of the present disclosure is preferably 0.03 μm or more and 0.30 μm or less. When the number-average diameter of the primary particles is within this range, the fine particles can be uniformly coated on the toner particles. Furthermore, stress on the toner can be suppressed, making it easier to achieve charge stability. If the number-average diameter of the primary particles of the fine particles is less than 0.03 μm, when a large number of images with low print density are output over a long period of time, the stress on the toner increases, which may cause the external additive particles to be easily embedded in the toner surface. Furthermore, if the number-average diameter of the primary particles exceeds 0.30 μm, the external additive particles may be easily detached from the toner surface. The number-average diameter of the primary particles of the external additive can be increased by lowering the reaction temperature, shortening the reaction time, or increasing the amount of catalyst in the hydrolysis and condensation steps. Furthermore, the number-average diameter of the primary particles of the fine particles can be decreased by increasing the reaction temperature, lengthening the reaction time, or reducing the amount of catalyst in the hydrolysis and condensation steps.

[0043] From the above viewpoint, the number average diameter of the primary particles of the external additive is more preferably 0.07 μm or more and 0.20 μm or less, and even more preferably 0.08 μm or more and 0.15 μm or less.

[0044] The Young's modulus of the external toner additive of the present disclosure is preferably 10 GPa or more and 30 GPa or less. When the Young's modulus is within this range, when the toner is subjected to stress from components such as the carrier, the stress can be alleviated, and the external additive can be further prevented from being embedded in the toner particle surface.

[0045] When the Young's modulus is 10 GPa or more, the external additive itself is less likely to be destroyed when the toner is subjected to stress from components such as the carrier. Furthermore, when the Young's modulus is 30 GPa or less, stress is more easily alleviated when the toner is subjected to stress from components such as the carrier, and the external additive can be more effectively prevented from being embedded in the toner particle surface. Therefore, the toner surface condition is less likely to change, and changes in the toner's chargeability and adhesive force can be more effectively prevented.

[0046] The Young's modulus of the external toner additive can be controlled by changing the mixing ratio of the alkoxysilane having the above structure, the temperature, time, pH, and type of catalyst in the hydrolysis and condensation steps. For example, if you want to increase the Young's modulus, you can increase the mixing ratio of the alkoxysilane having the above structure (a), decrease the mixing ratio of the alkoxysilane having the above structures (b) to (c), increase the temperature in the hydrolysis and condensation steps, extend the time for the hydrolysis and condensation steps, or increase the pH in the hydrolysis and condensation steps.

[0047] When it is desired to reduce the Young's modulus, it is possible to reduce the mixing ratio of the alkoxysilane having the above structure (a), increase the mixing ratio of the alkoxysilane having the above structures (b) to (c), lower the temperature in the hydrolysis step and the condensation step, shorten the time for the hydrolysis step and the condensation step, lower the pH in the hydrolysis step and the condensation step, etc. The Young's modulus of the external toner additive is more preferably 13 GPa or more and 20 GPa or less.

[0048] The external toner additive of the present disclosure is preferably a composite particle having fine particles A and fine particles B, wherein the fine particles A are particles having the organosilicon polymer already described, and the fine particles B are particles that exist at least partially embedded in the surface of the mother particle, fine particles A. By adopting a composite particle configuration, it is possible to improve the adhesion between the external additive and the toner particles, thereby improving the charging stability of the toner over the long term and further suppressing fluctuations in image density and color.

[0049] The Young's modulus of the fine particles B is preferably 50 GPa or more and 200 GPa or less. When the Young's modulus is within the above range, the external additive itself is less likely to be destroyed when the toner is subjected to stress from components such as the carrier, and the durability stability of the toner can be improved.

[0050] Furthermore, it is preferable that the fine particles B are present in a state where at least a portion thereof is embedded in the surface of the fine particles A, and the average embedding rate is 30% to 90%. When the average embedding rate is within the above range, the fine particles B are less likely to detach when the toner is subjected to stress from components such as the carrier, and contamination of the carrier and charging components can be suppressed. The embedding rate of the fine particles B can be controlled by the reaction time and reaction temperature with the alkoxysilane having the above structure. Methods for reducing the embedding rate include shortening the reaction time between the alkoxysilane and the fine particles B and lowering the reaction temperature. Methods for increasing the embedding rate include extending the reaction time between the alkoxysilane and the fine particles B and raising the reaction temperature.

[0051] As the fine particles B, inorganic fine particles or resin fine particles can be used, but silica fine particles such as colloidal silica are preferred in terms of preventing detachment from the fine particles A, which are organosilicon polymer particles.

[0052] When the external toner additive of the present disclosure is washed by the washing method described below, it is preferable that, in X-ray photoelectron spectroscopy measurement, the atomic concentration of silicon atoms is dSi, the atomic concentration of oxygen atoms is dO, and the atomic concentration of carbon atoms is dC, and the total of these is taken as 100 atomic %, the atomic concentration of carbon atoms bonded to silicon atoms is 30 atomic % or more, and the amount of silanol groups of the external toner additive, measured by titration using KOH, is 0.025 mmol / g or more and 0.800 mmol / g or less. Cleaning method: a) 10 g of the external toner additive is dispersed in 200 mL of hexane, and subjected to ultrasonic treatment (frequency 30 kHz, output capacity 15 W, intensity 100%, time 5 minutes). b) Distilling off hexane from the toner external additive dispersion.

[0053] Within the above range, the charge stability of the toner is improved over a long period of time, and fluctuations in image density and color can be suppressed. The amount of silanol groups in the external toner additive can be controlled by the mixing ratio of the alkoxysilane having the above structure, the temperature and time of the hydrolysis and condensation processes, the type and amount of surface treatment agent, and the processing conditions. For example, to increase the amount of silanol groups, methods include increasing the mixing ratio of the alkoxysilane having the above structure (a), decreasing the mixing ratio of the alkoxysilane having the above structures (b) to (c), increasing the temperature of the hydrolysis and condensation processes, and lengthening the time of the hydrolysis and condensation processes. To decrease the amount of silanol groups, methods include decreasing the mixing ratio of the alkoxysilane having the above structure (a), increasing the mixing ratio of the alkoxysilane having the above structures (b) to (c), decreasing the temperature of the hydrolysis and condensation processes, and shortening the time of the hydrolysis and condensation processes.

[0054] The content of the external toner additive of the present disclosure is preferably 0.1 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, relative to 100 parts by mass of toner particles, from the viewpoint of charge stability.

[0055] If the content of the external additive is less than 0.1 parts by mass, when a large amount of low-density images are output over a long period of time in a harsh environment such as a high-temperature, high-humidity environment, the stress on the toner cannot be suppressed, making it difficult to obtain the effect of durability stability. Also, if the content of the external additive is more than 20.0 parts by mass, filming of the external additive particles on the carrier, charging member, and photosensitive member may occur when images are output over a long period of time.

[0056] [Toner particles] Next, the configuration of the toner particles to which the external toner additive of the present disclosure is externally added will be described in detail.

[0057] <Binder resin> The binder resin contained in the toner particles is not particularly limited, and the following polymers or resins can be used.

[0058] Examples of suitable materials include homopolymers of styrene and its substituted derivatives, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers; and polyvinyl chloride, phenolic resins, naturally modified phenolic resins, naturally modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins. Among these, polyester resins are preferred from the viewpoints of durability and charging stability.

[0059] In addition, the acid value of the polyester resin is preferably 0.5 mgKOH / 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 the Si-CH3 in the fine particles interact with each other, further improving durability and toner charging performance under high-temperature and high-humidity environments. The acid value is more preferably 1 mgKOH / g or more and 20 mgKOH / g or less, and even more preferably 1 mgKOH / g or more and 15 mgKOH / g or less.

[0060] <Coloring agent> The toner particles may contain a colorant. Examples of the colorant include the following:

[0061] Examples of black colorants include carbon black and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the clarity from the viewpoint of the image quality of a full-color image.

[0062] Examples of pigments for magenta toner include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0063] Dyes for magenta toner include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0064] Examples of pigments for cyan toner include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; and CI Acid Blue 45, and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

[0065] An example of a dye for cyan toner is CI Solvent Blue 70.

[0066] Yellow toner pigments include the following: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Vat Yellow 1, 3, 20.

[0067] An example of a yellow toner dye is CI Solvent Yellow 162.

[0068] The content of the colorant is preferably 0.1 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0069] <Wax> The toner particles may contain wax. Examples of wax include the following.

[0070] Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or their block copolymers; waxes whose main component is fatty acid esters such as carnauba wax; partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0071] Further examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene Saturated fatty acid bisamides such as bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearyl isophthalamide; fatty metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.

[0072] The content of the wax is preferably 2.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0073] <Charge control agent> The toner particles may contain a charge control agent. Any known charge control agent can be used as the charge control agent contained in the toner, but a metal compound of an aromatic carboxylic acid is particularly preferred, as it is colorless, can charge the toner quickly, and can stably maintain a constant charge amount.

[0074] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate or sulfonate ester on the side chain, polymeric compounds having carboxylate or carboxylate ester on the side chain, boron compounds, urea compounds, silicon compounds, and calixarene. The charge control agent may be added internally or externally to the toner particles.

[0075] The amount of the charge control agent added is preferably 0.2 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0076] [Inorganic fine powder] In addition to the external toner additives described above, the toner of the present disclosure may also contain other inorganic fine powders as needed. The inorganic fine powders may be internally added to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powders such as silica are preferred. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0077] As an external additive to improve fluidity and durability, 2 / g or more 400m 2 / g or less of inorganic fine powder is preferred. The inorganic fine powder is preferably used in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of toner particles. When the above range is satisfied, the effect of durability and stability is easily obtained.

[0078] [Developer] The toner of the present disclosure can be used as a one-component developer, but is preferably mixed with a magnetic carrier and used as a two-component developer in terms of improving dot reproducibility and obtaining stable images over a long period of time.

[0079] Examples of magnetic carriers that can be used include generally known magnetic carriers such as surface-oxidized iron powder, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, oxide particles, and magnetic materials such as ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state.

[0080] When the toner is mixed with a magnetic carrier to be used as a two-component developer, good results are usually obtained when the carrier mixing ratio is, in terms of toner concentration in the two-component developer, preferably 2% by mass or more and 15% by mass or less, and more preferably 4% by mass or more and 13% by mass or less.

[0081] [Method of manufacturing toner particles and method of manufacturing toner] The method for producing toner particles is not particularly limited, and any of the conventionally known production methods such as suspension polymerization, emulsion aggregation, melt-kneading, and dissolution suspension methods can be used.

[0082] The toner particles thus obtained may be mixed with the external toner additive of the present disclosure, and, if necessary, other external additives, to obtain a toner. The toner particles may be mixed with the external toner additive of the present disclosure and other external additives using a mixing device such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0083] [Methods for measuring various physical properties] The methods for measuring various physical properties are explained below.

[0084] <Separation of External Additives and Toner Particles> It is also possible to measure each physical property using external additives separated from the toner by the following method.

[0085] Add 200 g of sucrose (manufactured by Kinoshita Chemical Co., Ltd.) to 100 mL of ion-exchanged water, and dissolve it while stirring in hot water to prepare a thick sucrose solution. Put 31 g of the thick sucrose solution and 6 mL of Contaminon N (a 10% by mass aqueous solution of a neutral detergent for precision measuring instruments with a pH of 7 composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) into a centrifuge tube to prepare a dispersion. Add 1 g of toner to this dispersion, and loosen the toner lumps with a spatula or the like.

[0086] Shake the centrifuge tube in the above shaker under the condition of 350 reciprocations per minute for 20 minutes. After shaking, transfer the solution to a glass tube (50 mL) for a swinging rotor, and perform centrifugation in a centrifuge under the conditions of 3500 rpm for 30 minutes. In the glass tube after centrifugation, toner exists in the uppermost layer, and fine particles exist on the aqueous solution side of the lower layer. Collect the aqueous solution of the lower layer, perform centrifugation to separate sucrose and fine particles, and collect the fine particles. If necessary, repeat centrifugation. After sufficient separation, dry the dispersion and collect the fine particles.

[0087] When a plurality of external additives are added, the external additives according to the present disclosure can be separated by using a centrifugation method or the like.

[0088] <Method for Measuring Carbon Concentration, Oxygen Concentration, and Silicon Concentration of External Additives Using ESCA> The method for measuring the carbon concentration, oxygen concentration, and silicon concentration on the surface of the external additive using ESCA is shown below.

[0089] The ESCA apparatus and measurement conditions are as follows. Apparatus: Quantum2000 (manufactured by ULVAC - PHI, Inc.) X-ray source: Monochromatized Al-Kα Sample measurement range: 100 μm in diameter Optoelectronic capture angle: 45° X-ray: 50μm 12.5W 15kV Raster: 300μm × 200μm PassEnergy: 46.95eV Step Size: 0.200eV Neutral electron gun: 20μA, 1V Ar ion gun: 7mA, 10V Number of sweeps: C 20 times, O 10 times, Si 15 times

[0090] As a measurement principle, photoelectrons are generated using an X-ray source, and the energy based on the unique chemical bonds of the substance is measured. From the peak intensity of each measured element, the surface atomic concentration (atomic %) is calculated using the relative sensitivity factor provided by PHI.

[0091] The ratio of carbon atoms is calculated as the ratio of the carbon concentration to the total of the carbon concentration, oxygen concentration, and silicon concentration (dC / (dC + dO + dSi) × 100).

[0092] <Method for measuring the amount of silanol groups of an external additive measured by titration using KOH> The amount of silanol groups of the external additive is measured by a method that improves the method of quantifying silanol groups by titration based on the shear method.

[0093] (Preparation of measurement solution) Put 2.0 g of the external additive and 25 g of ethanol into a 200 ml beaker, shake the beaker by hand to wet the external additive with ethanol. Then add 75 g of 20% NaCl aqueous solution and disperse the fine particles for 1 minute by ultrasonic dispersion. <000039q>

[0094] (Measurement) The external additive dispersion in the beaker is stirred with a stirrer. 0.1 mol / L HCl aqueous solution is added dropwise with a micropipette to adjust the pH to 4.0. 0.1 mol / L KOH solution is added dropwise as the titration solution, and the amount of 0.1 mol / L KOH added until the pH reaches 9.0 is taken as the amount of silanol groups (mmol / g). Specifically, the amount of silanol groups per unit mass of microparticles is calculated using the following formula: Amount of silanol groups (mmol / g) = Amount of KOH dropped (mmol) / 2.0 (g) (amount of sample particles)

[0095] <Method for measuring the number average particle size of primary particles of external additives> The number-average particle size of the primary particles of the external additive can be determined by centrifugal sedimentation. Specifically, 0.01 g of dried external additive particles was placed in a 25 mL glass vial, and 0.2 g of 5% Triton solution and 19.8 g of RO water were added to prepare a solution. Next, the probe (the innermost tip) of an ultrasonic disperser was immersed in the solution, and ultrasonic dispersion was performed at an output of 20 W for 15 minutes to obtain a dispersion. Subsequently, the number-average particle size of the primary particles was measured using a CPS Instruments DC24000 centrifugal sedimentation particle size distribution analyzer. The disk rotation speed was set to 18,000 rpm, and the true density was 1.3 g / cm. 3 Before the measurement, the instrument was calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0096] <Method for measuring Young's modulus of external additives> The Young's modulus of the external additive is determined by a microcompression test using a Hysitron PI 85L Pico Indenter (manufactured by BRUKER). The measurement conditions are as follows, and the Young's modulus (MPa) is calculated from the slope of the profile (load-displacement curve) of the displacement (nm) and test force (μN) obtained in the measurement. Equipment and fixtures Base system: Hysitron PI-85L Measurement indenter: 1 μm diameter circular flat-end indenter SEM used: Thermo Fisher Versa 3D SEM conditions: -10°tilt, 13pA at 10keV Measurement conditions Measurement mode: Displacement control Maximum displacement: 30nm Displacement speed: 1 nm / sec Hold time: 2 seconds Unloading speed: 5nm / sec ·Analysis method Hertz analysis is applied to the curve obtained when compressed from 0 nm to 10 nm in the load-displacement curve, and the Young's modulus of the fine particles is calculated. ·sample A silicon wafer with external additives attached thereto is used.

[0097] <Method for measuring Young's modulus of fine particle B> First, the composition of particle B is identified. Measurements are performed using a scanning electron microscope "S-4800" (trade name; manufactured by Hitachi, Ltd.). Those in which there is a difference in image contrast between the area originating from inorganic particle B and the area originating from organic particle A are classified as external additives for toner of the present invention, while those in which there is no such difference in contrast are classified as external additives other than the external additives for toner of the present invention. Note that inorganic particle B is observed to have higher brightness. The external additive is observed, and the compositions of particle A and particle B are identified using an energy dispersive X-ray analyzer at a maximum magnification of 2,000,000 times. After identifying the composition of particle B, fine particles with the same composition as particle B are prepared, and the Young's modulus of the external additive is measured in the same manner as in the measurement of the Young's modulus of the external additive described above, to determine the Young's modulus of particle B.

[0098] <Method for measuring the embedding rate of fine particle B> After thoroughly dispersing the external additive in a visible light-curable resin (product name: Aronix LCR Series D-800; manufactured by Toagosei Co., Ltd.), the resin is cured by irradiating it with short-wavelength light. The resulting cured product is cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin samples. The cut samples are then magnified 40,000 to 50,000 times using a transmission electron microscope (JEOL JEM-2800 electron microscope) (TEM-EDX) to observe the cross section of the external additive. The diameter of particle B and the depth of particle B embedded in particle A are measured from the cross-sectional image. Five particles of particle B are randomly selected for each particle of external additive, and the embedding rate of particle B is calculated using the following formula. The number of external additive particles analyzed was 20 or more, and the average value was used as the embedding rate of particle B. Burial rate of particle B (%) = (depth of particle B buried in particle A / diameter of particle B) x 100

[0099] <Solid 29 Method for measuring the content ratio of constituent compounds in organosilicon polymers using Si-NMR> solid 29 In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional groups bonded to Si in the constituent compounds of the organosilicon polymer. By identifying the position of each peak using a standard sample, the structure bonded to Si can be identified. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The ratio of the peak area of ​​the M unit structure, D unit structure (c), T unit structure (b), and Q unit structure (a) to the total peak area can be calculated.

[0100] If the external additive has inorganic silicon components such as silica particles on its surface in addition to the organosilicon polymer, the inorganic silicon components can be removed by adding the external additive to a strong alkaline (pH 12-14) solution and then centrifuging.

[0101] solid 29 The specific conditions for Si-NMR measurement are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DDMAS method 29Si 45° Sample tube: zirconia 3.2 mm diameter Sample: Filled in powder form into a test tube Sample rotation speed: 10kHz Relaxation delay: 180s Scan:2000

[0102] After the measurement, the peaks of a plurality of silane components of the sample having different substituents and bonding groups are separated into M unit structures, D unit structures, T unit structures, and Q unit structures by curve fitting, and the peak areas of each are calculated.

[0103] Curve fitting is performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series), software for the JNM-EX400 manufactured by JEOL Ltd. Click "1D Pro" from the menu icon to load the measurement data. Next, select "Curve fitting function" from "Command" on the menu bar to perform curve fitting. Curve fitting is performed for each component so that the difference (composite peak difference) between the composite peak obtained by curve fitting and the peak of the measurement results is minimized. Structure (1): Q unit structure Structure (2): D unit structure Structure (3): M-unit structure Structure (4): T unit structure

[0104] [ka]

[0105] In the structure, R1 to R6 represent alkyl groups with 1 to 6 carbon atoms bonded to silicon. The content of each structure in the organosilicon polymer is calculated from the peak area corresponding to each structure. If it is necessary to confirm the structure in more detail, 29 Along with the Si-NMR measurement results 13C-NMR and 1 The results of H-NMR measurements may also be used for identification.

[0106] <Measuring method for surface treatment agents of external additives> The surface treatment agent of the external additive is analyzed by pyrolysis GC-MS (gas chromatography mass spectrometry).

[0107] The specific measurement conditions are as follows. Equipment: GC6890A (Agilent), pyrolysis equipment (Japan Analytical Industry Co., Ltd.) Column: HP-5ms 30m Thermal decomposition temperature: 590℃ The surface treatment agent of the external additive is identified by identifying the position of each peak in the profile obtained by measurement using a standard sample.

[0108] <Method for measuring the acid value of binder resin> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid components, such as free fatty acids and resin acids, contained in 1 g of sample. The acid value is measured as follows in accordance with JIS-K0070-1992.

[0109] (1) Reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution.

[0110] Dissolve 7 g of special-grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide and leave for 3 days, then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The potassium hydroxide solution factor is determined by placing 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution to determine the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0111] (2) Operation (A) Main test A 2.0 g sample of crushed binder resin was weighed accurately into a 200 mL Erlenmeyer flask, and 100 mL of a 2:1 toluene / ethanol mixture was added and dissolved over 5 hours. A few drops of the phenolphthalein solution were then added as an indicator, and the solution was titrated with the potassium hydroxide solution. The titration endpoint was determined when the indicator remained a pale red color for approximately 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene / ethanol (2:1) mixed solution is used).

[0112] (3) The obtained results are substituted into the following formula to calculate the acid value. A=[(CB)×f×5.61] / S where A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

[0113] <Measurement of the acid value of polyester resin from toner> The acid value of the polyester resin from the toner can be measured by the following method: The polyester resin is separated from the toner by the following method, and the acid value is measured.

[0114] The toner is dissolved in tetrahydrofuran (THF), and the solvent is removed from the resulting soluble matter by distillation under reduced pressure to obtain the tetrahydrofuran (THF) soluble component of the toner.

[0115] The tetrahydrofuran (THF) soluble component of the obtained toner is dissolved in chloroform to prepare a sample solution with a concentration of 25 mg / ml.

[0116] 3.5 ml of the obtained sample solution is poured into the following apparatus, and resin components with a molecular weight of 2000 or more are separated under the following conditions. Preparative GPC device: Preparative HPLC LC-980 model manufactured by Japan Analytical Industry Co., Ltd. Preparative column: JAIGEL 3H, JAIGEL 5H (manufactured by Japan Analytical Industry Co., Ltd.) Eluent: chloroform Flow rate: 3.5ml / min

[0117] After separating the high molecular weight component derived from the resin, the solvent is distilled off under reduced pressure, and the residue is further dried under reduced pressure at 90° C. for 24 hours. The above procedure is repeated until about 2.0 g of the resin component is obtained.

[0118] Using the obtained sample, the acid value is measured according to the above procedure.

[0119] <Method for measuring weight average particle size (D4) of toner> The weight average particle diameter (D4) of the toner is calculated as follows. The measurement device used is a particle counting and analysis device "CDA-1000X" (manufactured by Sysmex Corporation) equipped with a 100 μm aperture tube and employing the pore electrical resistance method. The measurement conditions are set and the measurement data is analyzed using the accompanying dedicated software "CDA-1000X" (manufactured by Sysmex Corporation).

[0120] The aqueous electrolyte solution used for the measurement may be, for example, "Cell Pack" (manufactured by Sysmex Corporation).

[0121] Before carrying out the measurements and analysis, the dedicated software was set up as follows.

[0122] On the "measurement condition setting" screen of the dedicated software, set the total count number to 50,000, the number of repeated measurements to 1, and the measurement mode to total count (no limit).

[0123] The specific measurement method is as follows. (1) Pour approximately 150 ml of the electrolyte solution into a dedicated glass round-bottom beaker, set it on the sample stage, and stir with the stirring propeller at 500 rpm. Then, click "Blank Check Measurement" in the dedicated software to start the measurement and confirm that the count is less than 500. If the count is 500 or more, repeatedly clean the beaker and aperture. (2) Approximately 30 ml of the above-mentioned aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a dilution of Contaminon N (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted approximately three times by mass with ion-exchanged water is added as a dispersant. (3) Prepare an ultrasonic disperser "Ultrasonic Dispension System Tetra150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees. Place approximately 3.3 L of ion-exchanged water in the ultrasonic disperser's water tank and add approximately 2 mL of Contaminon N to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is being irradiated with ultrasonic waves, approximately 10 mg of toner is added little by little and dispersed, and the ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is adjusted appropriately to be between 10°C and 40°C. (6) Using a pipette, add the electrolyte solution (5) containing the dispersed toner to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to approximately 6%. Then, measure the particle count until it reaches 50,000 particles. (7) The measurement data is analyzed using the dedicated software provided with the device to calculate the weight average particle size (D4).

[0124] [Configuration included in the embodiment of the present invention] The disclosure of this embodiment includes the following configuration. (Configuration 1) An external toner additive containing an organosilicon polymer having a siloxane bond, In the external toner additive, when measured by X-ray photoelectron spectroscopy, the atomic concentration of silicon atoms is dSi, the atomic concentration of oxygen atoms is dO, and the atomic concentration of carbon atoms is dC, and the sum of these is taken as 100 atomic %, the atomic concentration of carbon atoms bonded to silicon atoms is 30 atomic % or more and 60 atomic % or less; the external toner additive has a silanol group amount of 0.025 mmol / g or more and 0.800 mmol / g or less, as measured by a titration method using KOH; Regarding the silicon atoms contained in the organosilicon polymer, the total number of silicon atoms is set to 1.00, and the Si a The ratio of silicon atoms represented by Pa is the ratio of Si in the structure represented by the above unit (b). b The ratio of silicon atoms represented by Pb and Si in the structure represented by the above unit (c) c The external toner additive is characterized in that, when the ratio of silicon atoms represented by the formula (1) is defined as Pc, Pa, Pb and Pc satisfy the following formulae (1) and (2): (1)(Pa)+(Pb)+(Pc)≧0.80 (2)(Pb)+(Pc)≧0.30 (Configuration 2) The external toner additive according to configuration 1, wherein the number average particle diameter of the primary particles of the external toner additive is 0.03 μm or more and 0.30 μm or less. (Configuration 3) The external toner additive according to configuration 1 or 2, wherein the external toner additive has a Young's modulus of 10 GPa or more and 30 GPa or less. (Configuration 4) The external toner additive according to any one of Configurations 1 to 3, wherein the external toner additive is a composite particle having fine particles A and fine particles B, the fine particles A being particles having the organosilicon polymer, and the fine particles B being particles present in a state where at least a portion of the particles is embedded in the surface of the fine particles A. (Configuration 5) The external toner additive according to Configuration 4, wherein the fine particles B are inorganic fine particles having a Young's modulus of 50 GPa or more and 200 GPa or less. (Configuration 6) The external toner additive according to Configuration 4 or 5, wherein the average embedding ratio of the fine particles B, represented by the following formula, is 30% or more and 90% or less. Burial rate of particle B (%) = (depth of particle B buried in particle A / diameter of particle B) x 100 (Configuration 7) The external toner additive cleaned by the cleaning method described below has, in X-ray photoelectron spectroscopy measurement, a ratio of the atomic concentration of carbon atoms bonded to silicon atoms of 30 atomic % or more, where dSi is the atomic concentration of silicon atoms, dO is the atomic concentration of oxygen atoms, and dC is the atomic concentration of carbon atoms, and the sum of these is taken as 100 atomic %, 7. The external toner additive according to any one of configurations 1 to 6, wherein the amount of silanol groups in the external toner additive measured by a titration method using KOH is 0.025 mmol / g or more and 0.800 mmol / g or less. Cleaning method: a) 10 g of the external toner additive is dispersed in 200 mL of hexane, and subjected to ultrasonic treatment (frequency 30 kHz, output capacity 15 W, intensity 100%, time 5 minutes). b) Distilling off hexane from the dispersion of the external additive for toner. (Configuration 8) A toner comprising toner particles and the external additive according to any one of Configurations 1 to 7. (Configuration 9) The toner according to Configuration 8, wherein the content of the external additive per 100 parts by weight of the toner particles is 0.1 parts by weight or more and 20.0 parts by weight or less. [Example]

[0125] The present invention will be described in more detail with reference to the following examples, which, however, are not intended to limit the scope of the present invention. Unless otherwise specified, the "parts" in the following formulations are all by mass.

[0126] <Production Example of Toner Additive 1> 1. Hydrolysis and condensation polymerization process (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 12.2 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) To this was added 2.0 g of 28% ammonia water, 15.0 g of tetraethoxysilane, and 5.0 g of colloidal silica aqueous dispersion A (silica solid content: 40 mass%, particle size: 40 nm), and the mixture was stirred at 30°C for 3.0 hours to obtain a raw material solution.

[0127] 2. Particulate process 120.0 g of RO water was placed in a 1000 ml beaker, and the raw material solution obtained in step 1 above was added dropwise over 5 minutes while stirring at 25°C. Thereafter, the mixture was heated to 60°C and stirred for 1.5 hours while maintaining the temperature at 60°C, thereby obtaining a dispersion of external additive fine particles.

[0128] 3. Surface treatment process To the dispersion of external additive fine particles obtained in the above 2. Granulation step, 3.0 g of tetraethoxysilane and 3.0 g of dimethyldimethoxysilane were added and stirred at 60°C for 3.0 hours. After leaving to stand for 5 minutes, the powder that settled at the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain external toner additive 1. The number average particle size of the primary particle size of external toner additive 1 was 0.12 μm.

[0129] <Production Example of Toner Additive 2> External toner additive 2 was obtained in the same manner as in the production example of external toner additive 1, except that in the above 3. surface treatment step, the stirring temperature was changed to 45° C. and the stirring time was changed to 1.0 hour.

[0130] <Production Example of Toner Additive 3> 1. Hydrolysis and condensation polymerization process (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 12.2 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) To this was added 2.0 g of 28% aqueous ammonia and 15.0 g of tetraethoxysilane, and the mixture was stirred at 30° C. for 2.0 hours. (3) Furthermore, 5.0 g of colloidal silica aqueous dispersion A (silica solid content: 40 mass %, particle size: 40 nm) was added and stirred for 10 minutes to obtain a raw material solution.

[0131] 2. Particulate process 120.0 g of RO water was placed in a 1000 ml beaker, and the raw material solution obtained in step 1 above was added dropwise over 5 minutes while stirring at 25°C. Thereafter, the mixture was heated to 60°C and stirred for 1.5 hours while maintaining the temperature at 60°C, thereby obtaining a dispersion of external additive fine particles.

[0132] 3. Surface treatment process To the dispersion of external additive fine particles obtained in the above 2. Granulation step, 3.0 g of tetraethoxysilane and 3.0 g of dimethyldimethoxysilane were added, and the mixture was stirred for 3.0 hours at 60° C. After leaving the mixture to stand for 5 minutes, the powder that precipitated at the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120° C. for 24 hours, to obtain external toner additive 3.

[0133] <Production Example of Toner Additive 4> External toner additive 4 was obtained in the same manner as in the production example of external toner additive 1, except that in (2) of the above 1. Hydrolysis and polycondensation step, the stirring temperature was changed to 45°C.

[0134] <Production Example of Toner Additive 5> External toner additive 5 was obtained in the same manner as in the production example of external toner additive 1, except that in (2) of the above 1. Hydrolysis and polycondensation step, a polyester resin fine particle dispersion (solid content: 25% by mass, particle size: 50 nm) was used instead of colloidal silica aqueous dispersion A.

[0135] <Production Example of Toner Additive 6> External toner additive 6 was obtained in the same manner as in the production example of external toner additive 1, except that colloidal silica aqueous dispersion A was not added in (2) of the above 1. Hydrolysis and polycondensation step.

[0136] <Production Example of Toner Additive 7> External toner additive 7 was obtained in the same manner as in the production example of external toner additive 1, except that in (1) of the above 1. Hydrolysis and polycondensation step, dimethyldimethoxysilane was changed to 12.7 g, and in (2) tetraethoxysilane was changed to 14.5 g.

[0137] <Production Example of Toner Additive 8> External toner additive 7 was obtained in the same manner as in the production example of external toner additive 1, except that in (1) of the above 1. Hydrolysis and polycondensation step, dimethyldimethoxysilane was changed to 7.2 g, and in (2) tetraethoxysilane was changed to 20.0 g.

[0138] <Production Example of Toner Additive 9> External toner additive 9 was obtained in the same manner as in the production example for external toner additive 1, except that in (1) of the above 1. Hydrolysis and polycondensation step, dimethyldimethoxysilane was changed to 7.2 g, and in (2), tetraethoxysilane was not added and 20.0 g of trimethoxymethylsilane was added.

[0139] <Production Example of Toner Additive 10> External toner additive 10 was obtained in the same manner as in the production example of external toner additive 1, except that in (1) of the above 1. Hydrolysis and polycondensation step, dimethyldimethoxysilane was changed to 3.2 g, and in (2) tetraethoxysilane was changed to 24.0 g.

[0140] <Production Example of Toner Additive 11> External toner additive 11 was obtained in the same manner as in the production example of external toner additive 1, except that in (2) of the above 1. Hydrolysis and polycondensation step, the amount of 28% ammonia water was changed to 1.0 g, the stirring temperature was changed to 40°C, and the stirring time was changed to 3.5 hours.

[0141] <Production Example of Toner Additive 12> External toner additive 12 was obtained in the same manner as in the production example of external toner additive 1, except that in (2) of the above 1. Hydrolysis and polycondensation step, the amount of 28% ammonia water was changed to 3.0 g and the stirring temperature was changed to 25°C.

[0142] <Production Example of Toner Additive 13> External toner additive 13 was obtained in the same manner as in the production example for external toner additive 1, except that in (2) of the above 1. Hydrolysis and polycondensation step, colloidal silica aqueous dispersion B (silica solid content: 40 mass %, particle size: 10 nm) was used instead of colloidal silica aqueous dispersion A, the amount of 28% ammonia water was changed to 1.0 g, the stirring temperature was changed to 45°C, and the stirring time was changed to 4.0 hours.

[0143] <Production Example of Toner Additive 14> External toner additive 14 was obtained in the same manner as in the production example of external toner additive 1, except that in (2) of the above 1. Hydrolysis and polycondensation step, the amount of 28% ammonia water was changed to 5.0 g, the stirring temperature was changed to 25°C, and the stirring time was changed to 2.0 hours.

[0144] <Production Example of Toner Additive 15> A 250 mL four-neck round-bottom flask equipped with an overhead stirrer, condenser, and thermocouple was charged with 18.7 g of Colloidal Silica Dispersion C (40 wt. % silica solids, 30 nm particle size), 125 mL of DI water, and 16.5 g (0.066 mol) of methacryloxypropyl-trimethoxysilane. The temperature was increased to 65°C, and the mixture was stirred at 120 rpm. Nitrogen gas was bubbled through the mixture for 30 minutes. After 3 hours, 0.16 g of 2,2'-azobisisobutyronitrile radical initiator dissolved in 10 mL of ethanol was added, and the temperature was increased to 75°C. The radical polymerization was allowed to proceed for 5 hours, after which 3 mL of 1,1,1,3,3,3-hexamethyldisilazane was added to the mixture, and the reaction was allowed to proceed for an additional 3 hours.

[0145] The final mixture was filtered through a 170 mesh sieve to remove any coagulum, and the dispersion was dried in a Pyrex dish at 120° C. overnight to obtain external toner additive 15.

[0146] <Production Example of Toner Additive 16> External toner additive 16 was obtained in the same manner as in the production example of external toner additive 1, except that tetraethoxysilane was not added in the above 3. surface treatment step.

[0147] <Production Example of Toner Additive 17> External toner additive 17 was obtained in the same manner as in the production example of external toner additive 1, except that in the above 3. Surface treatment step, the amount of tetraethoxysilane was changed to 6.0 g and the amount of dimethyldimethoxysilane was changed to 6.0 g.

[0148] <Production Example of Toner Additive 18> External toner additive 18 was obtained in the same manner as in the production example of external toner additive 1, except that in the above 3. surface treatment step, tetraethoxysilane and dimethyldimethoxysilane were not added, and 6.0 g of hexamethyldisilazane was added.

[0149] <Production Example of Toner Additive 19> External toner additive 19 was obtained in the same manner as in the production example of external toner additive 1, except that in (1) of the above 1. Hydrolysis and polycondensation step, dimethyldimethoxysilane was changed to 19.2 g, and in (2) tetraethoxysilane was changed to 8.0 g.

[0150] Table 1 shows the physical properties of external toner additives 1 to 19.

[0151] [Table 1]

[0152] In the table, the percentage of carbon atoms indicates the ratio of the carbon concentration to the sum of the carbon concentration, oxygen concentration, and silicon concentration measured by ESCA (dC / (dC+dO+dSi)×100), the amount of silanol groups indicates the amount of silanol groups per 1 g of external additive, and the particle size indicates the number-average particle size of the primary particles.

[0153] <Production Example of Polyester Resin A1> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 moles) Terephthalic acid (TPA) 25.0 parts (0.145 moles) Adipic acid 8.0 parts (0.054 moles) Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then purged with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 4 hours at 200°C while stirring (first reaction step). Then, 1.2 parts (0.006 mol) of trimellitic anhydride (TMA) was added, and the mixture was allowed to react for 1 hour at 180°C (second reaction step), yielding polyester resin A1, the binder resin component. The acid value of this polyester resin A1 was 5 mgKOH / g.

[0154] <Production Example of Polyester Resin A2> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts (0.155 moles) Terephthalic acid 24.1 parts (0.145 moles) Titanium tetrabutoxide 0.6 parts The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then purged with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 2 hours at 200°C while stirring. 5.8 parts (0.030 mol%) of trimellitic anhydride was then added, and the mixture was allowed to react for 10 hours at 180°C to obtain polyester resin A2, the binder resin component. The acid value of this polyester resin A2 was 10 mgKOH / g.

[0155] <Production Example of Toner Particle 1> Polyester resin A1 70.0 parts Polyester resin A2 30.0 parts Fischer-Tropsch wax (maximum endothermic peak temperature 78°C) 5.0 parts CI Pigment Blue 15:3 5.0 parts 0.1 parts of 3,5-di-t-butylsalicylic acid aluminum compound The raw materials shown in the above recipe were mixed in a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a rotation speed of 20 s -1 After mixing for 5 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 125°C and a rotation speed of 300 rpm. The resulting kneaded mixture was cooled and coarsely pulverized using a hammer mill to obtain a coarsely pulverized product with a diameter of 1 mm or less. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Corporation). Further, classification was carried out using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were a classification rotor rotation speed of 50.0 s -1 The resulting toner particles 1 had a weight average particle size (D4) of 5.9 μm.

[0156] <Toner 1 manufacturing example> 100 parts of toner particles Toner additive 1 6.0 parts The above materials were mixed in a Henschel mixer FM-10C (Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 30 s -1 The mixture was mixed for 10 minutes, and a toner 1 was obtained.

[0157] <Production Examples of Toners 2 to 23> Toners 2 to 23 were obtained in the same manner as in the production example of Toner 1, except that the external toner additives and the amounts added were changed as shown in Table 2. The physical properties of Toners 2 to 23 are shown in Table 2.

[0158] [Table 2]

[0159] <Carrier 1 manufacturing example> Number average particle size: 0.30 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m)2 / kg) of magnetite 1 Number average particle size: 0.50 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite2 To each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles.

[0160] Phenol: 10% by weight Formaldehyde solution: 6% by weight (40% formaldehyde, 10% methanol, 50% water) Magnetite treated with the above silane compound 1:58 mass% Magnetite treated with the above silane compound 2: 26 mass% The above materials, 5 parts of a 28% by weight aqueous ammonia solution, and 20 parts of water were placed in a flask, and the temperature was raised to 85°C over 30 minutes while stirring and mixing, and the temperature was maintained at 85°C for 3 hours to allow the polymerization reaction to proceed, resulting in hardening of the phenolic resin. The hardened phenolic resin was then cooled to 30°C, and water was added. The supernatant was removed, and the precipitate was washed with water and air-dried. This was then dried under reduced pressure (5 mmHg or less) at 60°C to obtain magnetic material-dispersed spherical carrier 1. The volume-based 50% particle size (D50) was 34.2 μm.

[0161] <Production example of two-component developer 1> To 92.0 parts of Carrier 1, 8.0 parts of Toner 1 were added and mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain Two-Component Developer 1.

[0162] <Production Examples of Two-Component Developers 2 to 23> Two-component developers 2 to 23 were obtained by carrying out the same production procedure as in the production example of two-component developer 1, except that toner 1 was changed to toners 2 to 23.

[0163] Example 1 <Toner evaluation method> Using a Canon full-color copier imagePress C800 as the image forming apparatus, two-component developer 1 was placed in a cyan developer container of the image forming apparatus, and the above toner was placed in a cyan toner container, and the evaluation described below was carried out.

[0164] The modification was to remove the mechanism that discharges excess magnetic carrier from the developing unit. The amount of toner on the paper in the FFh image (solid image) was 0.45 mg / cm. 2 FFh is the 256 gradations expressed in hexadecimal, with 00h being the first gradation of the 256 gradations (white background) and FF being the 256th gradation of the 256 gradations (solid area).

[0165] (1) Measurement of image density changes The evaluation paper was plain paper GF-C081 (A4, basis weight 81.4 g / m 2 (sold by Canon Marketing Japan Inc.) was used.

[0166] An image output test of 20,000 sheets was conducted with an image ratio of 80%. During the continuous printing of 20,000 sheets, the sheets were printed under the same development and transfer conditions (without calibration) as the first sheet.

[0167] The above test was conducted in a high-temperature, high-humidity environment (temperature 30°C, relative humidity 80%). Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), the initial density (first sheet) and the density of the 20,000th image printed at an image ratio of 80% were measured, and the difference Δ was used to rank the results according to the following criteria. A grade of D or higher was considered good. (Evaluation criteria: Image density difference) A: Δ is less than 0.02 B: Δ is 0.02 or more and less than 0.05 C: Δ is 0.05 or more and less than 0.10 D: Δ is 0.10 or more and less than 0.15 E: Δ is 0.15 or more

[0168] (2) Evaluation method for transferability after durability testing A solid image was output after 100,000 images were output at an image ratio of 1% in a high-temperature, high-humidity environment (temperature 30°C, relative humidity 80%). The residual toner remaining on the photosensitive drum after solid image formation was removed by taping it with transparent polyester adhesive tape.

[0169] The peeled adhesive tape was applied to a piece of paper, and the density was measured using a spectrodensitometer (500 series, X-Rite). In addition, the adhesive tape alone was applied to a piece of paper, and the density was also measured. The density difference Δ was calculated by subtracting the latter density value from the former density value, and this density difference Δ was evaluated based on the following evaluation criteria.

[0170] During the 100,000 consecutive image output, the images were output under the same development and transfer conditions (without calibration) as the first image. In the 100,000 image output durability test, the transfer material used for evaluation was plain copy paper CS-680 (A4 paper, basis weight: 68 g / m 2 (Sold by Canon Marketing Japan Inc.) was used for the solid image after the output test. Multi-Purpose Paper (commonly known as Voice Paper) (A4 size, basis weight: 75 g / m 2 (sold by Canon USA) was used.

[0171] The evaluation was as follows: D or higher was considered good. The evaluation results are shown in Table 3. (Evaluation criteria: density difference) A: Δ is less than 0.02 B: Δ is 0.02 or more and less than 0.05 C: Δ is 0.05 or more and less than 0.10 D: Δ is 0.10 or more and less than 0.15 E: Δ is 0.15 or more

[0172] Examples 2 to 18 Using two-component developers 2 to 18, evaluation was carried out in the same manner as in Example 1. The evaluation results of Examples 2 to 18 are shown in Table 3.

[0173] Comparative Examples 1 to 5 Using two-component developers 19 to 23, evaluations were carried out in the same manner as in Example 1. The evaluation results of Comparative Examples 1 to 5 are shown in Table 3.

[0174] [Table 3]

Claims

1. An external toner additive comprising an organosilicon polymer having a siloxane bond, In the external toner additive, when measured by X-ray photoelectron spectroscopy, the atomic concentration of silicon atoms is dSi, the atomic concentration of oxygen atoms is dO, and the atomic concentration of carbon atoms is dC, and the sum of these is taken as 100 atomic %, the atomic concentration of carbon atoms bonded to silicon atoms is 30 atomic % or more and 60 atomic % or less, the external toner additive has a silanol group amount of 0.025 mmol / g or more and 0.800 mmol / g or less, as measured by a titration method using KOH; Regarding the silicon atoms contained in the organosilicon polymer, the total number of silicon atoms is set to 1.00, and the number of Si atoms in the structure represented by the following unit (a) is a The ratio of silicon atoms represented by Pa is the ratio of Si in the structure represented by the following unit (b). b The ratio of silicon atoms represented by Pb and Si in the structure represented by the following unit (c) is c When the ratio of silicon atoms represented by the formula is Pc, The external toner additive is characterized in that Pa, Pb, and Pc satisfy the following formulae (1) and (2): (Pa)+(Pb)+(Pc)≧0.80 (1) (Pb)+(Pc)≧0.30 (2) 【Chemistry 1】 (R 1 , R 2 each independently represents an alkyl group having 1 to 6 carbon atoms.

2. The external toner additive according to claim 1, wherein the number average particle diameter of primary particles of the external toner additive is 0.03 μm or more and 0.30 μm or less.

3. 3. The external toner additive according to claim 1, wherein the external toner additive has a Young's modulus of 10 GPa or more and 30 GPa or less.

4. 3. The toner external additive according to claim 1, wherein the toner external additive is a composite particle having fine particles A and fine particles B, the fine particles A being particles having the organosilicon polymer, and the fine particles B being particles present in a state where at least a portion of the particles B is embedded in the surface of the fine particles A.

5. 5. The external toner additive according to claim 4, wherein the fine particles B are inorganic fine particles having a Young's modulus of 50 GPa or more and 200 GPa or less.

6. 5. The external toner additive according to claim 4, wherein the average embedding ratio of the fine particles B, represented by the following formula, is 30% or more and 90% or less. Buried rate of particle B (%) = (depth of particle B buried in particle A / diameter of particle B) × 100

7. The external toner additive washed by the washing method described below has, in X-ray photoelectron spectroscopy measurement, a ratio of the atomic concentration of carbon atoms bonded to silicon atoms of 30 atomic % or more, where dSi is the atomic concentration of silicon atoms, dO is the atomic concentration of oxygen atoms, and dC is the atomic concentration of carbon atoms, and the total of these is taken as 100 atomic %, 3. The external toner additive according to claim 1, wherein the amount of silanol groups in the external toner additive measured by a titration method using KOH is 0.025 mmol / g or more and 0.800 mmol / g or less. ・Cleaning method: a) 10 g of the external toner additive is dispersed in 200 mL of hexane, and subjected to ultrasonic treatment (frequency 30 kHz, output capacity 15 W, intensity 100%, time 5 minutes). b) Distilling off hexane from the dispersion of the external additive for toner.

8. A toner having toner particles and an external additive, the external additive comprises an organosilicon polymer having a siloxane bond, In X-ray photoelectron spectroscopy measurement of the external additive, when the atomic concentration of silicon atoms is dSi, the atomic concentration of oxygen atoms is dO, and the atomic concentration of carbon atoms is dC, the sum of which is taken as 100 atomic %, the proportion of the atomic concentration of carbon atoms bonded to silicon atoms is 30 atomic % or more and 60 atomic % or less; the external additive has a silanol group amount, as measured by a titration method using KOH, of 0.025 mmol / g or more and 0.800 mmol / g or less; Regarding the silicon atoms contained in the organosilicon polymer, the total number of silicon atoms is set to 1.00, and the number of Si atoms in the structure represented by the following unit (a) is a The ratio of silicon atoms represented by Pa is the ratio of Si in the structure represented by the following unit (b). b The ratio of silicon atoms represented by Pb and Si in the structure represented by the following unit (c) is c When the ratio of silicon atoms represented by the formula is Pc, The toner is characterized in that Pa, Pb, and Pc satisfy the following formulas (1) and (2): (1) (Pa)+(Pb)+(Pc)≧0.80 (2) (Pb)+(Pc)≧0.30 【Chemistry 2】 (R 1 , R 2 each independently represents an alkyl group having 1 to 6 carbon atoms.

9. 9. The toner according to claim 8, wherein the content of the external additive relative to 100 parts by mass of the toner particles is 0.1 parts by mass or more and 20.0 parts by mass or less.

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