External additive for toner and toner

Abstract

To provide an external additive for toner that has excellent electrification start-up properties, is excellent in durable stability, and with which high-quality images can be obtained over a long period.SOLUTION: An external additive for toner has external additive particles each having a base particle A and a plurality of convex forming particles B forming convex parts on the surface of the base particle A. The base particle A and the convex forming particle B are a particle having a silicon compound having a siloxane bond. A chemical bond is formed between the base particle A and the convex forming particle B. The total amount of specific formula units (a), (b) and (c) contained in the base particle A and the convex forming particle B is 80 mass% or more and 100 mass% or less. The external additive for toner has a Young's modulus of 10 GPa or more and 30 GPa or less. The external additive for toner has a number average particle diameter of 0.03 μm or more and 0.30 μm or less. When the number average particle diameter of the external additive for toner is defined as DA, and the average height of the convex parts on the surface of the external additive particles derived from the convex forming particles B as H, H / DA is 0.10 or more and 0.30 or less.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 2. Description of the Related Art In recent years, as full-color electrophotographic copying machines have come into widespread use, there has been an increasing demand for toners used in electrophotography to meet the demands of high-speed printing and to have a longer life. Conventionally, spherical silica and the like have been widely known as external additives used in toners. However, in environments where the toner comes into frequent contact with components such as carriers and is subjected to stress, such as when outputting images with low print density over a long period of time, the silica becomes embedded in the toner surface, causing a deterioration in the toner's adhesive strength, which has been an issue. Therefore, in order to prevent the embedding of the external additive, Patent Document 1 uses a silicone external additive to prevent embedding. Furthermore, in Patent Document 2, a mesh-like protrusion is provided to improve adhesion and suppress detachment. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6116711 [Patent Document 2] Patent No. 5522859 Summary of the Invention [Problem to be solved by the invention]

[0004] When silicone is used as an external additive as in Patent Document 1, embedding in the toner is suppressed, which reduces the contact area between the external additive and the toner matrix, and the external additive is detached from the toner matrix, leaving room for improvement. Also, in the case of a toner to which organic silicone fine particles having a network-like protrusion are externally added to improve detachment as in Patent Document 2, if the protrusions are low, the toner rolls on the surface of the toner matrix and moves toward the recesses, leaving room for improvement in terms of deterioration of the toner's adhesive force. Also, if the protrusions are high, there is room for improvement from the same perspective as with aggregated particles. An object of the present invention is to provide an external additive and a toner which solve the above problems. Specifically, the toner and the external additive have excellent durability and stability, are excellent in charge rise property, and can obtain high-quality images for a long period of time. [Means for solving the problem]

[0005] The present invention comprises: a plurality of protrusion-forming particles B which form protrusions on the surfaces of the base particles A; An external additive for toner having external additive particles having the following formula: the base particle A and the protrusion-forming particle B are particles having a silicon compound having a siloxane bond, and a chemical bond is formed between the base particle A and the protrusion-forming particle B, The base particle A has a total content of the following units (a), (b) and (c) of 80% by mass or more and 100% by mass or less, The convex-forming particles B have a total content of the following units (a), (b) and (c) of 80% by mass or more and 100% by mass or less, The Young's modulus of the toner external additive is 10 GPa or more and 30 GPa or less, The external toner additive has a number average particle diameter of 0.03 μm or more and 0.30 μm or less, the number average particle diameter of the external toner additive is DA, and the average height of the convex portions on the surface of the external additive particle originating from the convex-forming particles B is H, H / DA is 0.10 or more and 0.30 or less; The toner additive is characterized in that

[0006] [ka] (R1 and R2 each represent an alkyl group having 1 to 6 carbon atoms.) The present invention also provides a toner having toner particles and an external toner additive, the external toner additive having the above-mentioned structure. Effect of the Invention

[0007] The external toner additive of the present invention improves the durability and charge build-up properties of the toner, and enables stable, high-quality images to be obtained over a long period of time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In the present invention, the expressions "xx or more and xx or less" and "xx to xx" expressing a numerical range mean a numerical range including the lower and upper limit endpoints, unless otherwise specified.

[0009] The present inventors consider the mechanism by which the effects of the present invention are manifested as follows.

[0010] Particles having mesh-like protrusions, which have been used as external additives for toner, have been effective in improving adhesion to toner particles. However, particles with high mesh-like protrusions have a significantly reduced contact area with members such as carriers, making them difficult to charge. As a result, when an image with a high image ratio is output after an image with a low image ratio is output in a state in which the charge of the toner in the developing machine is saturated, the charge of the saturated toner in the developing machine and the charge of the toner newly supplied to the developing machine differ, resulting in a large change in density, and there is room for improvement. In addition, when particles with low mesh-like protrusions are deformed by rubbing against the carrier or members, the effect of the protrusions is hardly obtained, and they roll on the surface of the toner base and move toward the concave parts of the toner, so there is room for improvement in terms of developability and transferability due to the deterioration of the adhesion of the toner protrusions in contact with the carrier or members.

[0011] Therefore, the inventors of the present invention have found that the above-mentioned problems can be solved by forming the protrusions of the external additive as independent particle shapes on the external additive base and optimizing the size of the protrusions relative to the base particle diameter, and have arrived at the present invention. Although the mechanism is not clear, it is speculated that the independent protrusions and appropriate size increase the contact area with the toner base, suppressing the external additive from being liberated while also suppressing the external additive from rolling on the toner base, thereby maintaining good developability and transferability, and improving the charge rise by deformation during rubbing against the carrier or member.

[0012] [Toner additives] The toner external additive of the present invention comprises base particles A and a plurality of protrusion-forming particles B which form protrusions on the surfaces of the base particles A; An external additive for toner having external additive particles having the following formula: the base particle A and the protrusion-forming particle B are particles having a silicon compound having a siloxane bond, and a chemical bond is formed between the base particle A and the protrusion-forming particle B, The base particle A has a total content of the following units (a), (b) and (c) of 80% by mass or more and 100% by mass or less, The convex-forming particles B have a total content of the following units (a), (b) and (c) of 80% by mass or less and 100% by mass or less: The Young's modulus of the toner external additive is 10 GPa or more and 30 GPa or less, The external toner additive has a number average particle diameter of 0.03 μm or more and 0.30 μm or less, the number average particle diameter of the external toner additive is DA, and the average height of the convex portions on the surface of the external additive particle originating from the convex-forming particles B is H, H / DA is 0.10 or more and 0.30 or less; It is characterized by:

[0013] [ka] (R1 and R2 each represent an alkyl group having 1 to 6 carbon atoms.)

[0014] The number average particle diameter of the primary particles of the external toner additive of the present invention is 0.03 μm or more and 0.30 μm or less. When the number average particle diameter of the primary particles is within the above range, the fine particles can be uniformly coated on the toner particles. In addition, since the stress on the toner can be suppressed, the effect of charge stability is easily obtained. When the number average particle diameter of the primary particles of the fine particles is less than 0.03 μm, when a large amount of images with low print density are output for a long period of time, the stress on the toner increases, so that the external additive particles may be easily buried in the toner surface. In addition, when 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 particle diameter of the primary particles of the external additive can be increased by lowering the reaction temperature, shortening the reaction time, and increasing the amount of catalyst in the hydrolysis and condensation steps. In addition, the number average particle diameter of the primary particles of the fine particles can be decreased by increasing the reaction temperature, lengthening the reaction time, and decreasing the amount of catalyst in the hydrolysis and condensation steps.

[0015] From the above viewpoint, the number average particle size of the primary particles of the external additive 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.

[0016] The Young's modulus of the toner external additive of the present invention is 10 GPa or more and 30 GPa or less. When the Young's modulus is within the above range, when the toner is subjected to stress from a member such as a carrier, the stress is alleviated, and the external additive can be further prevented from being embedded in the toner particle surface.

[0017] 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 a member such as a carrier. Also, when the Young's modulus is 30 GPa or less, when the toner is subjected to stress from a member such as a carrier, the stress is easily alleviated, and the external additive can be more effectively prevented from being embedded in the toner particle surface. Therefore, the toner surface state is less likely to change, and changes in the chargeability and adhesive force of the toner can be more effectively prevented.

[0018] The Young's modulus of the toner external additive can be controlled by changing the mixing ratio of the monomers, the temperature, time, pH and type of catalyst in the hydrolysis and condensation steps. For example, when the Young's modulus is to be increased, the mixing ratio of the silane monomer having the above-mentioned (a) structure is increased, the mixing ratio of the silane monomer having the above-mentioned (b) and (c) structures is decreased, the temperature of the hydrolysis and condensation steps is increased, the time of the hydrolysis and condensation steps is increased, and the pH of the hydrolysis and condensation steps is increased. When the Young's modulus is to be decreased, the mixing ratio of the silane monomer having the above-mentioned (a) structure is decreased, the mixing ratio of the silane monomer having the above-mentioned (b) and (c) structures is increased, the temperature of the hydrolysis and condensation steps is decreased, the time of the hydrolysis and condensation steps is decreased, and the pH of the hydrolysis and condensation steps is decreased. The Young's modulus of the toner external additive is preferably 13 GPa or more and 20 GPa or less.

[0019] The total content of the following units (a), (b) and (c) in the base particles A and the convex forming particles B of the toner external additive of the present invention is 80% by mass or more and 100% by mass or less.

[0020] [ka] (R1 and R2 each represent an alkyl group having 1 to 6 carbon atoms.)

[0021] When the Young's modulus is within the above range, the external additive itself is not easily broken when the toner is subjected to stress from a member such as a carrier, and furthermore, the external additive has a suitable flexibility, so that the external additive can be prevented from being embedded in the toner particle surface. Therefore, the toner surface state is not easily changed, and changes in the chargeability and adhesive force of the toner can be further prevented. The content ratios of the above units (a), (b) and (c) in the external additive can be controlled by the amount of the above monomer added.

[0022] The content ratios of the above units (a), (b) and (c) in the base particles A and the convex forming particles B may be the same or different, so long as the Young's modulus can be set within the above range.

[0023] It is also preferable that the convex-forming particles B have a higher content ratio of the unit (a) than the mother particles A. When the convex-forming particles B contain more of the unit (a) than the mother particles A, the convex portions become appropriately hard, and the convex portions of the external additive are embedded in the toner particles, which further suppresses rolling and also suppresses detachment, which is preferable.

[0024] When the number average particle diameter of the external toner additive of the present invention is DA and the average height of the convex portion originating from the convex-forming particles B on the surface of the external additive particle is H, H / DA is 0.10 or more and 0.30 or less. When H / DA is in the above range, the adhesion of the external additive to the toner base is improved, detachment is suppressed, and rolling on the surface of the toner base is suppressed, so that a sufficient contact area is obtained during rubbing with the carrier or member, and the charge rise property can be improved. Furthermore, when H / DA is 0.15 or more and 0.25 or less, the above effect is more easily obtained, which is more preferable. The number average particle diameter DA of the external toner additive can be controlled by adjusting the reaction conditions in the hydrolysis and condensation steps described later. The average height H of the convex portion can be controlled by the particle diameter of the convex-forming particles B, the amount and time of addition of the convex-forming particles B during the production of the external toner additive, and the reaction time and reaction temperature of the convex-forming particles B and the monomer constituting the base particles A.

[0025] The methods for measuring the various physical properties will be described later.

[0026] <Manufacturing method> The method for producing the toner external additive of the present invention is not particularly limited, but it is preferable to form particles through hydrolysis and polycondensation of a silicon compound (silane monomer) by the sol-gel method. Specifically, it is preferable to produce base particles A by hydrolysis and polycondensation of a mixture of a bifunctional silane having two siloxane bonds and a tetrafunctional silane having four siloxane bonds, and to react fine particles (convex forming particles B) of a silicon compound having siloxane bonds prepared in advance by the same method thereto, thereby obtaining composite particles formed by forming chemical bonds between the base particles A and the convex forming particles B. Silane monomers such as bifunctional silane and tetrafunctional silane will be described later. The ratio of the bifunctional silane is preferably 30 mol% or more and 70 mol% or less, more preferably 40 mol% or more and 60 mol% or less. The ratio of the tetrafunctional silane is preferably 30 mol% or more and 80 mol% or less, more preferably 40 mol% or more and 70 mol% or less.

[0027] The toner external additive of the present invention is a particle having a silicon compound having a siloxane bond as a binder.

[0028] The method for producing the silicon compound according to the present invention is not particularly limited, and for example, a silane compound is dropped into water, hydrolyzed and condensed by a catalyst, and the resulting suspension is filtered and dried. The particle size can be controlled by the type of catalyst, the compounding ratio, the reaction start temperature, the dropping time, etc. As the catalyst, the acid catalyst includes hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, etc., and the basic catalyst includes ammonia water, sodium hydroxide, potassium hydroxide, etc., but is not limited thereto.

[0029] The silicon compound according to the present invention is preferably produced by the following method. Specifically, it is preferable to include the following steps: a first step of obtaining a hydrolyzate of a silicon compound; a second step of mixing the hydrolyzate with an alkaline aqueous medium and colloidal silica to polycondense the hydrolyzate and react it with colloidal silica; and a third step of mixing the polycondensation reaction product with an aqueous solution to form particles. In some cases, a hydrophobizing agent may be further added.

[0030] In the first step, in an aqueous solution in which an acidic or alkaline substance serving as a catalyst is dissolved in water, a silicon compound is contacted with the catalyst by a method such as stirring or mixing. Known catalysts can be suitably used. Specifically, examples of acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, and examples of basic catalysts include ammonia water, sodium hydroxide, and potassium hydroxide.

[0031] The amount of the catalyst used may be appropriately adjusted depending on the type of silicon compound and catalyst. Preferably, the amount of the catalyst used is 1×10 -3 The amount is selected from the range of 1 part by mass to 1 part by mass.

[0032] The amount of catalyst used is 1×10 -3 If the amount of catalyst 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 is low, making it easier to hydrolyze. The amount of water used is preferably 2 moles or more and 15 moles or less per mole of silicon compound. If the amount of water is 2 moles or more, the hydrolysis reaction proceeds sufficiently, and if it is 15 moles or less, productivity is improved.

[0033] The reaction temperature is not particularly limited and may be performed at room temperature or under heating, but since a hydrolysate can be obtained in a short time and a partial condensation reaction of the generated hydrolysate can be suppressed, it is preferable to carry out the reaction at a temperature maintained at 10 to 60° C. The reaction time is not particularly limited and may be appropriately selected in consideration of the reactivity of the silicon compound used, the composition of the reaction liquid obtained by mixing the silicon compound, the acid, and water, and the productivity.

[0034] 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. This produces a polycondensation reaction liquid. Here, the alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0035] 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 the first step and as a catalyst for the polycondensation reaction in the second step. 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.

[0036] The amount of the alkaline 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 alkaline 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.

[0037] 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.

[0038] Specific examples of the alcohol 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.

[0039] Among the organic solvents listed above, preferred are alcohol solvents such as methanol, ethanol, 2-propanol, butanol, etc. 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.

[0040] In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. As the aqueous solution, water (tap water, pure water, etc.) can be suitably used, but a component that is compatible with water, such as a salt, an acid, an alkali, an organic solvent, a surfactant, or a water-soluble polymer, may be further added to the water. The temperature of the polycondensation reaction liquid and the aqueous solution when they are mixed is not particularly limited, and is suitably selected in the range of 5 to 70°C in consideration of their composition, productivity, etc.

[0041] The method for recovering particles can be any known method without any particular limitation. For example, the method of scooping floating powder or the filtration method can be mentioned, but the filtration method is preferred because of its simple operation. The filtration method is not particularly limited, and a known device such as vacuum filtration, centrifugal filtration, or pressure filtration may be selected. The filter paper, filter, filter cloth, etc. used in filtration are not particularly limited as long as they are industrially available, and may be appropriately selected according to the device used.

[0042] The monomer to be used can be appropriately selected depending on its compatibility with the solvent and catalyst, its hydrolysis property, and the like. Examples of the tetrafunctional silane monomer having the above (a) structure include tetramethoxysilane, tetraethoxysilane, and tetraisocyanatesilane, and among these, tetraethoxysilane is preferred.

[0043] 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, ethoxymethoxysilane, ethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxyhydroxy ...methoxyhydroxysilane, ethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysil Examples of the 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.

[0044] Examples of the bifunctional silane monomer having the above (c) structure include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, and the like. Of these, dimethyldimethoxysilane is preferred.

[0045] <Other properties of toner additives> The true specific gravity of the toner external additive of the present invention is 1.00 g / cm 3 More than 1.60g / cm 3 Within the above range, when the toner is subjected to stress from a member such as a carrier, the external additive can be prevented from being embedded in the toner particle surface and from being destroyed. The true specific gravity of the external additive can be controlled by the amount of fine particles B added. The true specific gravity of the external additive for toner is 1.20 g / cm 3 More than 1.40g / cm 3 It is more preferable that:

[0046] In the toner external additive of the present invention, when the average height H of the convex portion derived from the convex-forming particle B is taken as DB, the H / DB ratio is preferably 0.30 or more and 0.50 or less. Within the above range, sufficient adhesion of the external additive to the toner base body is obtained and rolling is also suppressed, which is preferable. If it is less than 0.30, rolling cannot be sufficiently suppressed, and if it is more than 0.50, the contact area with the toner base body decreases and the external additive is likely to become detached. H / DB can be controlled by the particle size of the convex-forming particle B, the amount and time of addition of the convex-forming particle B during production of the toner external additive, and the reaction time and reaction temperature of the convex-forming particle B and the monomer constituting the base particle A.

[0047] The toner external additive of the present invention is preferably surface-treated with a hydrophobizing agent. The hydrophobizing agent is not particularly limited, but is preferably an organosilicon compound.

[0048] Examples of the compound include alkylsilazane compounds such as hexamethyldisilazane, alkylalkoxysilane compounds such as diethyldiethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, and butyltrimethoxysilane, fluoroalkylsilane compounds such as trifluoropropyltrimethoxysilane, chlorosilane compounds such as dimethyldichlorosilane and trimethylchlorosilane, siloxane compounds such as octamethylcyclotetrasiloxane, silicone oils, and silicone varnishes.

[0049] The hydrophobic treatment of the surface of the toner additive can suppress the change in the adhesion of the toner after durability testing. Among these, it is preferable that the fine particles are surface-treated with at least one compound selected from the group consisting of an alkylsilazane compound, an alkylalkoxysilane compound, a chlorosilane compound, a siloxane compound, and a silicone oil. Furthermore, it is more preferable that the toner additive is surface-treated with an alkylsilazane compound from the above viewpoint.

[0050] The contents of the above units (a), (b) and (c) in the base particles A and the convex forming particles B of the toner external additive of the present invention preferably satisfy the following formulae (I), (II) and (III). 0.30≦(a) / ((a)+(b)+(c))≦0.80···(I) 0≦(b) / (a)+(b)+(c)≦0.50 ···(II) 0.20≦(c) / (a)+(b)+(c)≦0.70 (III)

[0051] Within the above range, when the toner is subjected to stress from a member such as a carrier, it is possible to suppress embedding of the external additive in the surface of the toner particles and damage to the external additive itself. 0.40≦(a) / ((a)+(b)+(c))≦0.70···(I´) 0≦(b) / (a)+(b)+(c)≦0.10 ···(II´) 0.30≦(c) / (a)+(b)+(c)≦0.60 ···(III´) In this case, the amount of Si-CH3 present in the external additive becomes optimal, which is more preferable from the viewpoint of the durability and stability of the toner.

[0052] The content ratio in the base particles A and the convex-forming particles B may be the same or may be different as long as it is within the above range.

[0053] The content of the toner external additive of the present invention is preferably 0.1 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of toner particles from the viewpoint of charging stability, 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.

[0054] If the content of the external additive is less than 0.1 parts by mass, when a large amount of images with low print density are output for a long time under a harsh environment such as a high temperature and high humidity environment, the stress on the toner cannot be suppressed, and the effect of durability stability is difficult to obtain. 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 for a long time.

[0055] [Toner particles] Next, the constitution of the toner particles to which the fine particles of the present invention are externally added will be described in detail.

[0056] <Binding resin> The binder resin used in the toner of the present invention is not particularly limited, and the following polymers or resins can be used.

[0057] For example, homopolymers of styrene and its substitutes such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, and styrene-acrylonitrile-indene copolymer are usable as styrene-based copolymers; polyvinyl chloride, phenolic resin, naturally modified phenolic resin, naturally modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, and petroleum-based resin can be used. Among them, polyester resin is preferred from the viewpoint of durability and electrostatic stability.

[0058] 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, and the durability and the toner charging property in a high temperature and high humidity environment can be further improved. 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.

[0059] <Coloring agent> The toner of the present invention may contain a colorant, if necessary. Examples of the colorant include the following.

[0060] Examples of black colorants include carbon black, and a mixture of a yellow colorant, a magenta colorant, and a cyan colorant toned to black. 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 of the colorant from the viewpoint of the image quality of a full-color image.

[0061] Magenta toner pigments include the following: 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.

[0062] Dyes for magenta toners include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Violet 1; 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, 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0063] Pigments for cyan toners include the following: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Vat Blue 6; CI Acid Blue 45; copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

[0064] Cyan toner dyes include CI Solvent Blue 70.

[0065] Yellow toner pigments include: 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.

[0066] Yellow toner dyes include CI Solvent Yellow 162.

[0067] 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.

[0068] <Wax> The toner of the present invention may contain wax, if necessary. Examples of the wax include the following.

[0069] Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes whose main component is fatty acid esters such as carnauba wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0070] Further examples include the following: 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 alcohol, 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 alcohol, 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.

[0071] 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.

[0072] <Charge control agent> The toner of the present invention may contain a charge control agent as necessary. Any known charge control agent may 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, has a high charging speed, and can stably maintain a constant charge amount.

[0073] 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 calixarenes. The charge control agent may be added internally or externally to the toner particles.

[0074] 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.

[0075] <Inorganic fine powder> In addition to the above-mentioned external additives for toner, other inorganic fine powders may be used in combination with the toner of the present invention as necessary. The inorganic fine powders may be added internally to the toner particles, or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powders such as silica are preferred. The inorganic fine powders are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0076] As an external additive to improve fluidity, 2 / g or more 400m 2 In order to simultaneously improve the flowability and stabilize the durability, inorganic fine particles having a specific surface area within the above range may be used in combination.

[0077] The inorganic fine powder is preferably used in an amount of 0.1 parts by mass to 10.0 parts by mass based on 100 parts by mass of the toner particles. When the above range is satisfied, the effect of durability and stability is easily obtained.

[0078] <Developer> The toner of the present invention can be used as a one-component developer, but in order to further improve dot reproducibility, it is preferable to mix it with a magnetic carrier and use it as a two-component developer, in that stable images can be obtained over a long period of time. That is, it is preferable that the toner is the toner of the present invention, which is a two-component developer containing a toner and a magnetic carrier.

[0079] Examples of magnetic carriers that can be used include generally known magnetic carriers such as iron powder with an oxidized surface, 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, magnetic materials such as ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) that contain 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, in terms of the toner concentration in the two-component developer, is 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 the 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 fine external additive particles of the present invention and, if necessary, other external additives to obtain a toner. The toner particles, the fine external additive particles of the present invention, and other external additives may be mixed using a mixing device such as a double con mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0083] [Measurement methods for various physical properties] The methods for measuring various physical properties are described below.

[0084] <Separation of fine particles and toner particles from toner> The various physical properties can also be measured using fine particles separated from the toner by the following method.

[0085] About 30 ml of the electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and 6 mL of "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments with a pH of 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) is added as a dispersant to prepare a dispersion. 1 g of toner is added to this dispersion, and the toner clumps are loosened with a spatula or the like. A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and two oscillators with an oscillation frequency of 50 kHz built in with a phase shift of 180 degrees, and about 2 ml of the Contaminon N is added to this water tank. The beaker containing the dispersion with the toner added is set in an ultrasonic disperser, and the ultrasonic disperser is operated to liberate fine particles from the toner. Next, a diaphragm type dry vacuum pump DTC-41 (manufactured by ULVAC) is connected to the Kiriyama funnel and suction bell, and the toner particles and fine particles are filtered using Kiriyama funnel filter paper No. 5C. The fine particles are collected by settling the dispersion liquid in which the collected fine particles are dispersed using a centrifuge. If necessary, centrifugation is repeated to thoroughly separate the fine particles, and then the fine particles are collected and dried to obtain the fine particles.

[0086] When a plurality of external additives are added, the external additive of the present invention can be selected by adjusting the rotation speed of the centrifuge and separating the mixture.

[0087] <Method for measuring number average particle size DA of primary particles of external additives> The number-average particle size DA of the primary particles of the external additive can be determined by measurement using the centrifugal sedimentation method. 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 tip of the tip) of an ultrasonic disperser was immersed in the above solution, and ultrasonic dispersion was performed for 15 minutes at an output of 20 W to obtain a dispersion. Next, the number-average particle size of the primary particles was measured using this dispersion using a CPS Instruments centrifugal sedimentation particle size distribution analyzer DC24000. The disk rotation speed was set to 18,000 rpm, and the true density was 1.3 g / cm. 3 Prior to the measurement, the instrument was calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0088] <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).

[0089] 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.

[0090] 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 preparation Fine particles are attached to a silicon wafer.

[0091] <Method of measuring the average height H and maximum average diameter DB of the convex portions derived from the convex-forming particles B> The average height H and maximum average diameter DB of the convex portions derived from the convex-forming particles B are measured using a scanning electron microscope "S-4800" (product name; manufactured by Hitachi, Ltd.). 200 convex portions are randomly observed in a field of view where the external additive is magnified 200,000 times, the maximum diameter of each convex portion derived from the convex-forming particles is measured, and the maximum average diameter DB is calculated from the average value. In addition, when observing the 200 convex portions, the microscope is tilted to adjust the angle to a position where the height of the convex portions can be measured, the height of each convex portion is measured, and the average height H is calculated from the average value.

[0092] <Method for measuring true specific gravity of external additives> The true specific gravity of the external additive was measured by a dry automatic density meter Autopycnometer (manufactured by Yuasa Ionics Co., Ltd.) under the following conditions. Cell: SM cell (10ml) Sample size: 0.05g This measurement method is based on the gas phase displacement method to measure the true density of solids and liquids. Like the liquid phase displacement method, it is based on Archimedes' principle, but since gas (argon gas) is used as the displacement medium, it has high accuracy for measuring minute pores.

[0093] <Measuring method for surface treatment agents of external additives> The surface treatment agents of the external additives are analyzed by pyrolysis GC-MS (gas chromatography mass spectrometry).

[0094] Specifically, the measurement conditions are as follows. Equipment: GC6890A (Agilent), pyrolysis equipment (Japan Analytical Industry Co., Ltd.) Column: HP-5ms 30m Thermal decomposition temperature: 590℃ The position of each peak in the profile obtained by measurement is identified using a standard sample, thereby identifying the surface treatment agent of the external additive.

[0095] <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 a sample. The acid value is measured in accordance with JIS-K0070-1992 as follows.

[0096] (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.

[0097] 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 factor of the potassium hydroxide solution 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, and then calculating 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.

[0098] (2) Operation (A) Main Test 2.0 g of the crushed sample is accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a toluene / ethanol (2:1) mixed solution is added and dissolved for 5 hours. Next, several drops of the phenolphthalein solution are added as an indicator, and the potassium hydroxide solution is used for titration. The end point of the titration is when the indicator remains a light red color for about 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).

[0099] (3) The obtained result is substituted into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S Here, 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).

[0100] <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.

[0101] The toner is dissolved in tetrahydrofuran (THF), and the solvent is removed from the resulting soluble matter by distillation under reduced pressure to obtain a tetrahydrofuran (THF) soluble component of the toner.

[0102] The tetrahydrofuran (THF) soluble component of the obtained toner is dissolved in chloroform to prepare a sample solution having a concentration of 25 mg / ml.

[0103] 3.5 ml of the obtained sample solution is poured into the following apparatus, and resin components with molecular weights 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 Nippon Analytical Industry Co., Ltd.) Eluent: Chloroform Flow rate: 3.5ml / min After separating out the high molecular weight components derived from the resin, the solvent is distilled off under reduced pressure, and the mixture is dried for 24 hours under reduced pressure at 90°C. The above operation is repeated until about 2.0 g of the resin component is obtained. The acid value of the obtained sample is measured according to the above procedure.

[0104] <Method of measuring weight average particle size (D4) of toner particles> The weight-average particle diameter (D4) of the toner particles is measured with an effective measurement channel count of 25,000 channels using a precision particle size distribution measuring device using the narrow hole electrical resistance method, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube, and the accompanying dedicated software for setting measurement conditions and analyzing measurement data, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.), and the measurement data is analyzed and calculated.

[0105] The electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter).

[0106] Before carrying out the measurements and analyses, the dedicated software is set up as follows.

[0107] In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, set the total count number in the control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. In addition, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the aperture tube flush after measurement.

[0108] In the "Pulse to particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

[0109] The specific measurement method is as follows. (1) Pour about 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, remove dirt and air bubbles from inside the aperture tube using the "Aperture Tube Flush" function of the dedicated software. (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 solution prepared by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, with a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant. (3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) that has two oscillators with an oscillation frequency of 50 kHz built in with a phase shift of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the Conaminon N is added to this water tank. (4) The beaker (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolyte solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower. (6) Using a pipette, the electrolytic solution (5) in which the toner is dispersed is dropped into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to about 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume%, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4).

[0110] [Configuration included in the embodiment of the present invention] The disclosure of this embodiment includes the following configuration. (Configuration 1) Mother particle A, a plurality of protrusion-forming particles B which form protrusions on the surfaces of the base particles A; An external additive for toner having external additive particles having the following formula: the base particle A and the protrusion-forming particle B are particles having a silicon compound having a siloxane bond, and a chemical bond is formed between the base particle A and the protrusion-forming particle B, the total content of the units (a), (b) and (c) in the base particle A is 80% by mass or more and 100% by mass or less; the total content of the units (a), (b) and (c) in the protrusion-forming particles B is 80% by mass or more and 100% by mass or less, The Young's modulus of the toner external additive is 10 GPa or more and 30 GPa or less, The external toner additive has a number average particle diameter of 0.03 μm or more and 0.30 μm or less, the number average particle diameter of the external toner additive is DA, and the average height of the convex portions on the surface of the external additive particle originating from the convex-forming particles B is H, H / DA is 0.10 or more and 0.30 or less; 1. An external toner additive comprising: (Configuration 2) The external toner additive according to Configuration 1, wherein when the average maximum diameter of the convex-forming particles B is represented by DB, and H is the average height of the convex portions, H / DB is 0.30 or more and 0.50 or less. (Configuration 3) The external toner additive according to configuration 1 or 2, wherein the H / DA is 0.15 or more and 0.25 or less. (Configuration 4) The toner external additive according to any one of Configurations 1 to 3, wherein the contents of the units (a), (b) and (c) in the base particle A and the convex-forming particle B satisfy the following formulas (I), (II) and (III): 0.30≦(a) / ((a)+(b)+(c))≦0.80···(I) 0≦(b) / ((a)+(b)+(c))≦0.50 ···(II) 20≦(c) / ((a)+(b)+(c))≦0.70 ···(III) (Configuration 5) The toner external additive according to any one of Configurations 1 to 4, wherein the content of the unit (a) in the convex-forming particles B is higher than the content of the unit (a) in the base particles A. (Configuration 6) A toner comprising toner particles and the external toner additive according to any one of Configurations 1 to 5. (Configuration 7) The toner according to Configuration 6, wherein the content of the external toner additive relative to 100 parts by weight of the toner particles is 0.1 parts by weight or more and 20.0 parts by weight or less. EXAMPLES

[0111] The present invention will be described in more detail with reference to the following examples. However, these examples are not intended to limit the present invention. In the following formulations, "parts" are all by weight unless otherwise specified.

[0112] <Production Example of Dispersion of Convex Forming Particles B-1> B-1. Hydrolysis and polycondensation process: (B-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. (B-2) 1.0 g of 28% aqueous ammonia and 15.0 g of tetraethoxysilane were added thereto and stirred at 30° C. for 3.5 hours to obtain a raw material solution.

[0113] B-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 thereto over a period of 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 projecting particles B-1.

[0114] <Production Example of Dispersion of Convex Forming Particles B-2> A convex-forming particle B-2 dispersion liquid was obtained in the same manner as in the production example for the convex-forming particle B-1 dispersion liquid, except that in the above hydrolysis and polycondensation step (B-1), dimethyldimethoxysilane was not added, and 25.3 g of trimethoxymethylsilane was added, and in (B-2), tetraethoxysilane was changed to 1.9 g.

[0115] <Production Example of Dispersion of Convex Forming Particles B-3> A projection-forming particle B-3 dispersion was obtained in the same manner as in the production example of the projection-forming particle B-1 dispersion, except that in the hydrolysis and polycondensation step (B-2), the stirring time was changed to 4.0 hours.

[0116] <Production Example of Dispersion of Convex Forming Particles B-4> A projection-forming particle B-4 dispersion was obtained in the same manner as in the production example for projection-forming particle B-1 dispersion, except that in the hydrolysis and polycondensation step (B-2), the amount of 28% ammonia water was changed to 2.0 g and the temperature was changed to 35° C.

[0117] <Production Example of Dispersion of Convex-Forming Particles B-5> A projection-forming particle B-5 dispersion liquid was obtained in the same manner as in the production example of the projection-forming particle B-1 dispersion liquid, except that in the hydrolysis and polycondensation step (B-2), the temperature was changed to 35°C.

[0118] <Production Example of Dispersion of Convex Forming Particles B-6> A projection-forming particle B-6 dispersion was obtained in the same manner as in the production example of the projection-forming particle B-1 dispersion, except that in the hydrolysis and polycondensation step (B-2), the stirring time was changed to 3.0 hours.

[0119] <Production Example of Dispersion of Convex Forming Particles B-7> A projection-forming particle B-7 dispersion liquid was obtained in the same manner as in the production example of the projection-forming particle B-1 dispersion liquid, except that in the hydrolysis and polycondensation step (B-2), the temperature was changed to 45°C.

[0120] <Production Example of Dispersion of Convex Forming Particles B-8> A projection-forming particle B-8 dispersion was obtained in the same manner as in the production example of the projection-forming particle B-1 dispersion, except that in the hydrolysis and polycondensation step (B-2), the temperature was changed to 35° C. and the stirring time was changed to 4.0 hours.

[0121] <Production Example of Dispersion of Protruding Particles B-9> A convex-forming particle B-9 dispersion liquid was obtained in the same manner as in the production example for the convex-forming particle B-1 dispersion liquid, except that in (B-1) of the above hydrolysis and polycondensation step, dimethyldimethoxysilane was not added, and 8.2 g of trimethoxymethylsilane was added, and in (B-2) the amount of tetraethoxysilane was changed to 19.0 g.

[0122] <Production Example of Dispersion of Convex Forming Particle B-10> A projection-forming particle B-10 dispersion was obtained in the same manner as in the production example of the projection-forming particle B-1 dispersion, except that in the hydrolysis and polycondensation step (B-2), the temperature was changed to 45° C. and the stirring time was changed to 4.0 hours.

[0123] <Production Example of Dispersion of Convex Forming Particles B-11> A convex-forming particle B-11 dispersion liquid was obtained in the same manner as in the production example for the convex-forming particle B-1 dispersion liquid, except that in the above hydrolysis and polycondensation step (B-2), the amount of 28% ammonia water was changed to 2.0 g, the temperature was changed to 35° C., and the stirring time was changed to 3.0 hours.

[0124] <Production Example of Dispersion of Protruding Particles B-12> A convex-forming particle B-12 dispersion liquid was obtained in the same manner as in the production example for the convex-forming particle B-1 dispersion liquid, except that in (B-1) of the above hydrolysis and polycondensation step, dimethyldimethoxysilane was changed to 5.4 g, and in (B-2), tetraethoxysilane was not added and 21.8 g of trimethoxymethylsilane was added.

[0125] <Production Example of Dispersion of Convex Forming Particles B-13> A convex-forming particle B-13 dispersion liquid was obtained in the same manner as in the production example for the convex-forming particle B-1 dispersion liquid, except that in (B-1) of the above hydrolysis and polycondensation step, dimethyldimethoxysilane was not added, and 5.4 g of trimethoxymethylsilane was added, and in (B-2) tetraethoxysilane was changed to 21.8 g.

[0126] <Production Example of Toner Additive 1> 1. Hydrolysis and polycondensation 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) 2.0 g of 28% aqueous ammonia and 15.0 g of tetraethoxysilane were added thereto and stirred at 35° C. for 3.5 hours to obtain a raw material solution.

[0127] 2.Particleization process: 120.0 g of RO water was placed in a 1000 ml beaker, and the raw material solution obtained in the hydrolysis and polycondensation steps was added dropwise over 5 minutes while stirring at 25° C. Thereafter, the mixture was heated to 60° C. and stirred for 0.5 hours while maintaining the temperature at 60° C., at which point 180 g of the projection-forming particle B-1 dispersion was added dropwise, and the mixture was further stirred for 1.0 hour to obtain a dispersion of external additive fine particles.

[0128] 3. Hydrophobization process: 6.0 g of hexamethyldisilazane was added as a hydrophobizing agent to the dispersion liquid of the external additive fine particles obtained in the above-mentioned granulation step, and the mixture was stirred at 60° C. for 3.0 hours. 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 1. The number average particle diameter of the primary particle diameter of external toner additive 1 was 0.12 μm.

[0129] <Production Example of Toner Additive 2> In the above hydrolysis and polycondensation step (1), dimethyldimethoxysilane was changed to 5.4 g, and in (2), tetraethoxysilane was changed to 8.2 g, and 13.6 g of trimethoxymethylsilane was added. Except for this, an external toner additive 2 was obtained in the same manner as in the production example of external toner additive 1.

[0130] <Production Example of Toner Additive 3> External toner additive 3 was obtained in the same manner as in the production example for external toner additive 1, except that in (1) of the above hydrolysis and polycondensation step, dimethyldimethoxysilane was not added and 25.3 g of trimethoxymethylsilane was added, in (2) tetraethoxysilane was changed to 1.9 g, and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-2 dispersion liquid.

[0131] <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 the projection-forming particle B-1 dispersion liquid dropped in the above-mentioned granulation step was changed to the projection-forming particle B-3 dispersion liquid.

[0132] <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 the projection-forming particle B-1 dispersion liquid dropped in the above-mentioned granulation step was changed to the projection-forming particle B-4 dispersion liquid.

[0133] <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 the projection-forming particle B-1 dispersion liquid dropped in the above-mentioned granulation step was changed to the projection-forming particle B-5 dispersion liquid.

[0134] <Production Example of Toner Additive 7> External toner additive 7 was obtained in the same manner as in the production example for external toner additive 1, except that in the above-mentioned granulation process, the time for dropping the convex-forming particles was changed to dropping after stirring for 0.75 hours, the convex-forming particle B-1 dispersion liquid to be dropped was changed to convex-forming particle B-5 dispersion liquid, and the stirring time after dropping was changed to 0.75 hours.

[0135] <Production Example of Toner Additive 8> External toner additive 8 was obtained in the same manner as in the production example for external toner additive 1, except that in the above granulation process, the time for dropping the convex-forming particles was changed to dropping after stirring for 0.75 hours, the convex-forming particle B-1 dispersion liquid to be dropped was changed to convex-forming particle B-6 dispersion liquid, and the stirring time after dropping was changed to 0.75 hours.

[0136] <Production Example of Toner Additive 9> External toner additive 9 was obtained in the same manner as in the production example of external toner additive 1, except that in the above hydrolysis and polycondensation step (2), 28% ammonia water was changed to 3.0 g, the stirring temperature was changed to 25° C., and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-4 dispersion liquid.

[0137] <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 the above hydrolysis and polycondensation step (2), 28% ammonia water was changed to 1.0 g, the stirring temperature was changed to 40°C, and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-7 dispersion liquid.

[0138] <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 the above hydrolysis and polycondensation step (2), 28% ammonia water was changed to 3.0 g, the stirring temperature was changed to 35°C, and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-4 dispersion liquid.

[0139] <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 the above hydrolysis and polycondensation step (2), 28% ammonia water was changed to 1.0 g, the stirring temperature was changed to 30°C, and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-8 dispersion liquid.

[0140] <Production Example of Toner Additive 13> External toner additive 13 was obtained in the same manner as in the production example of external toner additive 1, except that the projection-forming particle B-1 dispersion liquid dropped in the above-mentioned granulation step was changed to the projection-forming particle B-9 dispersion liquid.

[0141] <Production Example of Toner Additive 14> Toner additive 14 was obtained in the same manner as in the production example of toner additive 1, except that in the above hydrolysis and polycondensation step (1), dimethyldimethoxysilane was changed to 2.7 g, and in (2), tetraethoxysilane was not added, and 24.5 g of trimethoxymethylsilane was added.

[0142] <Production Example of Toner Additive 15> External toner additive 15 was obtained in the same manner as in the production example of external toner additive 1, except that in (1) of the above hydrolysis and polycondensation step, dimethyldimethoxysilane was not added and 8.2 g of trimethoxymethylsilane was added, in (2) tetraethoxysilane was changed to 19.0 g, and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-9 dispersion liquid.

[0143] <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 in the above-mentioned granulation process, the time for dropping the convex forming particles was changed to immediately after the temperature reached 60°C and the stirring time after dropping was changed to 1.5 hours.

[0144] <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-mentioned granulation process, the time for dropping the convex forming particles was changed to dropping after stirring for 1.0 hour, and the stirring time after dropping was changed to 0.5 hour.

[0145] <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 hydrolysis and polycondensation step (2), the amount of 28% ammonia water was changed to 1.0 g, the stirring temperature was changed to 45° C., the stirring time was changed to 4.0 hours, and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-10 dispersion liquid.

[0146] <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 the above hydrolysis and polycondensation step (2), the amount of 28% ammonia water was changed to 5.0 g, the stirring temperature was changed to 25° C., the stirring time was changed to 2.0 hours, and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-11 dispersion liquid.

[0147] <Production Example of Toner Additive 20> External toner additive 20 was obtained in the same manner as in the production example of external toner additive 1, except that in (1) of the above hydrolysis and polycondensation step, dimethyldimethoxysilane was changed to 5.4 g, in (2) tetraethoxysilane was not added and 21.8 g of trimethoxymethylsilane was added, and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-12 dispersion liquid.

[0148] <Production Example of Toner Additive 21> External toner additive 21 was obtained in the same manner as in the production example of external toner additive 1, except that in (1) of the above hydrolysis and polycondensation step, dimethyldimethoxysilane was not added and 5.4 g of trimethoxymethylsilane was added, in (2) tetraethoxysilane was changed to 21.8 g, and the convex-forming particle B-1 dispersion liquid dropped in the above granulation step was changed to the convex-forming particle B-13 dispersion liquid.

[0149] The physical properties of each of the obtained toner external additives 1 to 21 are shown in Table 1.

[0150] [Table 1-1]

[0151] [Table 1-2]

[0152] <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, and a thermometer, stirring rod, condenser, and nitrogen inlet tube were attached and placed in a mantle heater. Next, the atmosphere in the flask was replaced with nitrogen gas, and the temperature was gradually raised while stirring, and the mixture was reacted for 4 hours while stirring at a temperature of 200°C (first reaction step). Then, 1.2 parts (0.006 moles) of trimellitic anhydride (TMA) was added, and the mixture was reacted for 1 hour at 180°C (second reaction step), to obtain polyester resin A1, which is a binder resin component. The acid value of this polyester resin A1 was 5 mgKOH / g.

[0153] <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, and a thermometer, stirring rod, condenser, and nitrogen inlet tube were attached and placed in a mantle heater. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually raised while stirring, and the mixture was reacted for 2 hours while stirring at a temperature of 200°C. Then, 5.8 parts (0.030 mol%) of trimellitic anhydride was added, and the mixture was reacted for 10 hours at 180°C to obtain polyester resin A2, which is a binder resin component. The acid value of this polyester resin A2 was 10 mgKOH / g.

[0154] <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 at 125°C, the mixture was kneaded in a twin-screw kneader (PCM-30, Ikegai Corp.) set at a temperature of 125°C and a rotation speed of 300 rpm. The kneaded mixture was cooled and coarsely pulverized in a hammer mill to a diameter of 1 mm or less to obtain a coarsely pulverized product. The coarsely pulverized product was finely pulverized in a mechanical pulverizer (T-250, Freund Turbo Corp.). Classification was further carried out using a rotary classifier (200TSP, Hosokawa Micron Corp.) to obtain toner particles 1. The operating conditions of the rotary classifier (200TSP, Hosokawa Micron Corp.) 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.

[0155] <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 Industry Co., Ltd.) at a rotation speed of 30 s-1 The mixture was mixed at 10 minutes rotation time to obtain toner 1.

[0156] <Toner 2-25 Manufacturing Example> Toners 2 to 25 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 25 are shown in Table 2.

[0157] [Table 2]

[0158] <Production example of carrier 1> Number average particle size 0.30μm (magnetization strength 65Am under a magnetic field of 1000 / 4π(kA / m) 2 / kg) of magnetite 1 Number average particle size 0.50μm (magnetization strength 65Am under a magnetic field of 1000 / 4π(kA / m) 2 / kg) of magnetite 2 To 100 parts of 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.

[0159] Phenol: 10% by weight Formaldehyde solution: 6% by mass (40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water) Magnetite treated with the above silane compound 1:58 mass% Magnetite treated with the above silane compound 2: 26% by mass 100 parts of the above material, 5 parts of 28% by mass ammonia solution, and 20 parts of water were placed in a flask, and the temperature was raised to 85°C in 30 minutes and maintained at 85°C while stirring and mixing, and a polymerization reaction was carried out for 3 hours to harden the resulting phenolic resin. The hardened phenolic resin was then cooled to 30°C, and water was added, after which the supernatant liquid was removed, and the precipitate was washed with water and then air-dried. This was then dried at a temperature of 60°C under reduced pressure (5 mmHg or less) to obtain a spherical magnetic carrier 1. The 50% particle diameter (D50) based on volume was 34.2 μm.

[0160] <Production example of two-component developer 1> Toner 1 (8.0 parts) was added to Carrier 1 (92.0 parts), and the mixture was mixed in a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain two-component developer 1.

[0161] <Production examples of two-component developers 2 to 25> Two-component developers 2 to 25 were obtained by carrying out the same production procedure as in the production example of two-component developer 1, except that the toner was changed as shown in Table 3.

[0162] [Table 3]

[0163] Example 1 <Toner Evaluation Method> A Canon full-color copier imagePress C800 was used as the image forming apparatus. The above two-component developer 1 was placed in a cyan developer container of the image forming apparatus, and the above toner 1 was placed in a cyan toner container, and the evaluation described below was performed.

[0164] The modification was to remove the mechanism that discharges excess magnetic carrier from the developer. The amount of toner on the paper in a FFh image (solid image) is 0.45 mg / cm 2 FFh is the hexadecimal value of 256 gradations, with 00h being the 1st gradation (white background) of the 256 gradations, and FF being the 256th gradation (solid area) of the 256 gradations.

[0165] (1) Measurement of image density change at 5% image ratio 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 10,000 sheets was performed with an image ratio of 5%. During the continuous printing of 10,000 sheets, the sheets were printed under the same development and transfer conditions (without calibration) as the first sheet.

[0167] The above test was carried out under normal temperature and humidity conditions (temperature 25°C, relative humidity 55%). Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), the initial (first sheet) density and the density of the 10,000th sheet printed at an image ratio of 5% were measured, and the difference Δ was used to rank the images according to the following criteria. A grade of C or higher was judged to be good.

[0168] (Evaluation standard: Image density difference Δ) A: Less than 0.02 B: 0.02 or more and less than 0.05 C: 0.05 or more and less than 0.10 D:0.10 or more

[0169] (2) Evaluation method for charge build-up in a normal temperature and low humidity environment The charge rise property was evaluated by measuring the change in density when images with different image printing ratios were output. An image with a low image ratio was output to saturate the charge of the toner in the developing machine, and then an image with a high image ratio was output. Then, a density change occurs due to the difference in charge between the saturated toner in the developing machine and the toner newly supplied to the developing machine. Toner with a fast charge rise becomes saturated as soon as it is supplied to the developing machine, so there is little change in density. On the other hand, toner with a slow charge rise takes time to become saturated after being supplied to the developing machine, so the charge amount of the entire toner decreases and the density changes.

[0170] First, an image output test of 1000 sheets was performed at an image ratio of 1%. During the continuous printing of 1000 sheets, the sheets were printed under the same developing conditions and transfer conditions (without calibration) as the first sheet. After that, an image output test of 1000 sheets was performed at an image ratio of 80%. During the continuous printing of 1000 sheets, the sheets were printed under the same developing conditions and transfer conditions (without calibration) as the first sheet. The image density of the 1000th sheet printed at an image ratio of 1% was taken as the initial density, and the density of the 1000th image printed at an image ratio of 80% was measured and evaluated according to the following evaluation criteria. The above test was performed in a normal temperature and low humidity environment (N / L; temperature 23°C, relative humidity 5%).

[0171] (Measurement of Image Density Change) Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), the density of the initial density and the 1000th image printed at an image ratio of 80% were measured, and the difference in image density was ranked according to the following criteria. C or higher was judged to be good.

[0172] (Evaluation standard: concentration difference Δ) A: Less than 0.02 B: 0.02 or more and less than 0.05 C: 0.05 or more and less than 0.10 D:0.10 or more

[0173] (3) Evaluation method for transferability after durability test In a room temperature and low humidity environment (temperature 25°C, relative humidity 5%), after outputting 100,000 images at an image ratio of 1%, a solid image was output. The residual toner remaining on the photoconductor (photoconductor drum) after the solid image formation was taped off with a transparent polyester adhesive tape.

[0174] 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 the 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.

[0175] During the continuous output of 100,000 images, 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, Inc.) was used. The evaluation is as follows. C or above is considered to be good.

[0176] (Evaluation standard: concentration difference Δ) A: Less than 0.02 B: 0.02 or more and less than 0.05 C: 0.05 or more and less than 0.10 D:0.10 or more

[0177] The above evaluation results are shown in Table 4.

[0178] [Examples 2 to 19] The two-component developers 2 to 19 were each evaluated in the same manner as in Example 1. The evaluation results of Examples 2 to 19 are shown in Table 4.

[0179] [Comparative Examples 1 to 6] The two-component developers 20 to 25 were each evaluated in the same manner as in Example 1. The evaluation results of Comparative Examples 1 to 6 are shown in Table 4.

[0180] [Table 4]

Claims

1. Mother particle A, a plurality of protrusion-forming particles B that form protrusions on the surfaces of the base particles A; An external additive for toner having external additive particles having the formula: the base particles A and the projecting particles B are particles having a silicon compound having a siloxane bond, and a chemical bond is formed between the base particles A and the projecting particles B, The total content of the following units (a), (b), and (c) in the base particles A is 80% by mass or more and 100% by mass or less: The convex-forming particles B have a total content of the following units (a), (b), and (c) of 80% by mass or more and 100% by mass or less: the Young's modulus of the external toner additive is 10 GPa or more and 30 GPa or less; the external toner additive has a number average particle size of 0.03 μm or more and 0.30 μm or less; where DA is the number average particle diameter of the external toner additive and H is the average height of the convex portions on the surface of the external additive particles originating from the convex-forming particles B, H / DA is 0.10 or more and 0.30 or less; 1. An external additive for toner comprising: 【Chemistry 1】 (R 1 , R 2 represents an alkyl group having 1 to 6 carbon atoms.

2. 2. The external toner additive according to claim 1, wherein when DB is the average maximum diameter of the convex-forming particles B and H is the average height of the convex portions, H / DB is 0.30 or more and 0.50 or less.

3. 3. The external toner additive according to claim 1, wherein the H / DA is 0.15 or more and 0.25 or less.

4. 3. The external toner additive according to claim 1, wherein the content ratios of the units (a), (b) and (c) in the base particles A and the convex-forming particles B satisfy the following formulas (I), (II) and (III): 0.30≦(a) / ((a)+(b)+(c))≦0.80...(I) 0≦(b) / ((a)+(b)+(c))≦0.50...(II) 0.20≦(c) / ((a)+(b)+(c))≦0.70...(III)

5. 3. The external toner additive according to claim 1, wherein the content of the unit (a) in the convex-forming particles B is higher than the content of the unit (a) in the base particles A.

6. A toner comprising toner particles and the external toner additive according to claim 1 or 2.

7. 7. The toner according to claim 6, wherein the content of the external toner 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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