Toner additive and toner

Abstract

To provide an external additive for toner that can improve separability without impairing developability.SOLUTION: An external additive for toner has oil and organic silicon polymer particles with pores. The external additive for toner contains the oil in an amount of 5.0 pts.mass or more and 20.0 pts.mass or less based on 100 pts.mass of the organic silicon polymer particles. The number average particle diameter of primary particles of the external additive for toner is 0.05 μm or more and 0.30 μm or less. When the BET specific surface area of the external additive for toner is defined as X(m2 / g), the BET specific surface area of the external additive for toner after washing obtained by washing the external additive for toner with hexane is defined as Y(m2 / g), and a theoretical BET specific surface area calculated from the particle diameter of the external additive for toner after washing is defined as Z(m2 / g), the following formulas (i) and (ii) are satisfied. (i) 1.8≤Y / X≤15.0; (ii)3.0≤Y / Z≤9.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an external additive for a toner and a toner used in an electrophotographic system. [Background technology]

[0002] In recent years, high levels of media compatibility are being demanded for toners used in POD (on-demand) printers, among others. Among these, separation (anti-wrapping) during the fixing process for thin paper is a particular issue. Conventionally, in order to improve separability, it has been common to improve wax seepage by adjusting the type and amount of wax in the toner matrix. In addition, a technique for improving separability by incorporating silicone oil into the toner matrix is ​​also known (Patent Document 1). Also known is a technique for introducing silicone oil into the interior or surface of an external additive that is added to the toner matrix by treating the external additive with silicone oil (Patent Documents 2 and 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2014-191107 A [Patent Document 2] JP 2016-138035 A [Patent Document 3] Patent Publication No. 2021-47351 Summary of the Invention [Problem to be solved by the invention]

[0004] As in Patent Document 1, when wax or oil is introduced into the toner matrix, the separation effect (the effect of preventing paper wrapping) may not be fully exhibited depending on the combination with the resin. Therefore, if the wax or oil content is increased to improve the separation effect, the carrier and components may be contaminated, resulting in a problem of deterioration in developability. Furthermore, even if an attempt is made to achieve a separation effect by introducing oil into an external additive instead of the toner matrix, as in Patent Documents 2 and 3, there is still the problem that the developability deteriorates due to contamination. An object of the present invention is to provide an external toner additive and a toner that solve the above-mentioned problems, specifically, to provide an external toner additive and a toner that can improve separability without impairing developability. [Means for solving the problem]

[0005] The present invention provides an external toner additive comprising pore-containing organosilicon polymer particles and oil, the organosilicon polymer particles contain 5.0 parts by weight or more and 20.0 parts by weight or less of oil per 100 parts by weight of the organosilicon polymer particles, the number average particle size of the primary particles of the external toner additive is 0.05 μm or more and 0.30 μm or less; The BET specific surface area of ​​the toner external additive is X (m 2 / g), and the BET specific surface area of ​​the external toner additive after washing obtained by washing the external toner additive with hexane is Y(m 2 / g), and the theoretical BET specific surface area calculated from the particle size of the external toner additive after washing is Z (m 2 / g), The external toner additive is characterized by satisfying the following formulae (i) and (ii): (i) 1.8≦Y / X≦15.0 (ii) 3.0≦Y / Z≦9.0 The present invention also provides a toner having toner particles and an external toner additive, The toner is characterized in that the external toner additive is an external toner additive having the above-described structure. [Effects of the Invention]

[0006] When the external toner additive of the present invention is used, the separation property of the toner can be improved without impairing the developability. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 2 is an explanatory diagram of a heat treatment apparatus used in the production of the toner of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] In the present invention, 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 invention are manifested is as follows.

[0010] Conventionally, silica particles used as external toner additives have almost no pores inside, so when oil treatment is performed, most of the oil is introduced onto the particle surface. In order to improve the separation property, a small amount of oil treatment is not effective, so a large amount of oil treatment is required, but this results in the particle surface being covered with a large amount of oil, which contaminates the carrier and components and deteriorates development.

[0011] On the other hand, if an organosilicon polymer has pores, the oil can be introduced into the pores, allowing for a large amount of oil to be introduced while minimizing exposure of the oil to the surface.The oil in the pores then seeps out onto the image surface in response to the heat and pressure during fixing, improving separability without impairing developability, which is what led to the present invention.

[0012] [Toner additives] The external toner additive of the present invention is an external toner additive comprising pore-containing organosilicon polymer particles and oil, the organosilicon polymer particles contain 5.0 parts by weight or more and 20.0 parts by weight or less of oil per 100 parts by weight of the organosilicon polymer particles, the number average particle size of the primary particles of the external toner additive is 0.05 μm or more and 0.30 μm or less; The BET specific surface area of ​​the toner external additive is X (m 2 / g), and the BET specific surface area of ​​the external toner additive after washing obtained by washing the external toner additive with hexane is Y(m 2 / g), and the theoretical BET specific surface area calculated from the particle size of the external toner additive after washing is Z (m 2 / g), It is characterized by satisfying the following formulas (i) and (ii). (i) 1.8≦Y / X≦15.0 (ii) 3.0≦Y / Z≦9.0 The external toner additive of the present invention contains silicon polymer particles having siloxane bonds, and the silicon polymer particles preferably contain 90% by mass or more, more preferably 95% by mass or more of silicon polymer.

[0013] The method for producing silicon polymer particles is not particularly limited, and 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, and examples of basic catalysts include, but are not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0014] Silicon polymer particles are preferably produced by the following method.Specifically, it preferably comprises 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 subjecting the hydrolyzate to a polycondensation reaction; and a third step of mixing the polycondensation reaction product with an aqueous solution to form particles.In some cases, a hydrophobic agent may be further added to the spherical silicon polymer particle dispersion to obtain hydrophobic spherical silicon polymer particles.

[0015] 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.

[0016] 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.

[0017] The amount of catalyst used is 1×10 -3 If the amount of catalyst used is 1 part by mass or more, the reaction will proceed sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the silicon polymer 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] The silicon polymer particles can be recovered by any known method without any particular limitations. For example, floating powder can be scooped out or a filtration method can be used, 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 in filtration are not particularly limited as long as they are industrially available, and can be selected appropriately depending on the device used.

[0027] The silicon polymer particles may be surface-treated with a known means such as a silane coupling agent or silicone oil to adjust the degree of hydrophobicity. The monomer to be used can be appropriately selected based on its compatibility with the solvent and catalyst, its hydrolysis property, etc. Examples of tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanatesilane, with tetraethoxysilane being preferred.

[0028] Trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, and methyldiethoxyhydroxysilane. silane, 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.

[0029] Examples of bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and dimethyldimethoxysilane, with dimethyldimethoxysilane being preferred.

[0030] Examples of monofunctional silanes include t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, and triphenylethoxysilane.

[0031] The external toner additive of the present invention contains oil, and its content is 5.0 to 20.0 parts by weight per 100 parts by weight of organosilicon polymer particles. If the oil content is less than 5.0 parts by weight, the amount of oil that seeps onto the image surface even when pressure is applied during fixing is insufficient, resulting in no separation effect. If the oil content is more than 20.0 parts by weight, the pores alone cannot retain all the oil, and the oil is exposed to the surface, causing contamination and deteriorating developability. The oil content is preferably in the range of 8.0 to 15.0 parts by weight, more preferably 10.0 to 12.0 parts by weight.

[0032] The number-average particle size of the primary particles of the external toner additive in the present invention is 0.05 μm or more and 0.30 μm or less. If the number-average particle size is less than 0.05 μm, oil is less likely to seep out even when pressure is applied during fixing, resulting in no separation effect. If the number-average particle size is greater than 0.30 μm, the external additive is not fixed to the toner, so the external additive is not transported to the fixing process, resulting in no separation effect. The preferred range of the number-average particle size is 0.08 μm or more and 0.15 μm or less, and more preferably 0.10 μm or more and 0.13 μm or less.

[0033] In a wet production method, the average particle size of an external toner additive can be controlled by the hydrolysis and condensation conditions during the reaction (reaction temperature, reaction time, stirring time), pH, and type of catalyst. For example, methods for increasing the average particle size include lowering the temperature during the hydrolysis reaction, shortening the stirring time, lowering the pH of the solution, and increasing the pH of the solution during condensation. Methods for decreasing the average particle size include raising the temperature during the hydrolysis reaction, lengthening the stirring time, raising the pH of the solution, and lowering the pH of the solution during condensation.

[0034] The BET specific surface area of ​​the external toner additive of the present invention is X (m 2 / g), and the BET specific surface area of ​​the external toner additive after washing obtained by washing the external toner additive with hexane is Y(m 2 / g), X and Y are 1.8≦Y / X≦15.0 It is necessary to satisfy the relationship shown below. When the pores of the external additive are filled with oil by oil treatment, the BET specific surface area changes compared to before treatment. Therefore, the degree of change in this BET specific surface area can be used as an indicator of how much the pores are filled with oil. The BET specific surface area (Y) before treatment can be determined by washing the external additive with hexane after oil treatment to remove the oil. When Y / X is less than 1.8, the pores are hardly filled with oil, resulting in no separation effect. When Y / X is greater than 15.0, the pore volume of the external additive is too large, resulting in low strength of the external additive itself and easy destruction by even slight external force. This causes oil to leak out during processes prior to fixing, contaminating components and deteriorating developability. The preferred range for Y / X is 3.0≦Y / X≦10.0, and more preferably 4.5≦Y / X≦8.0.

[0035] Furthermore, the theoretical BET specific surface area calculated from the particle size of the external additive for toner after washing is expressed as Z (m 2 / g), Y and Z are 3.0≦Y / Z≦9.0 It is necessary to satisfy the relationship shown below. An external additive that satisfies this relationship is porous and can contain a sufficient amount of oil inside. When Y / Z is less than 3.0, the external additive is not porous, so oil cannot be introduced into the interior, and the oil is exposed to the surface, resulting in contamination and deterioration of developability. When Y / Z is greater than 9.0, the pore volume of the external additive is too large, so the strength of the external additive itself is low, and even a slight external force can cause oil to escape in processes prior to fixing, contaminating components and the like, thereby deteriorating developability. The preferred range for Y / Z is 4.0≦Y / Z≦8.0, and more preferably 5.0≦Y / Z≦7.0.

[0036] Y / X can be controlled by changing the processing conditions for Y / Z and the oil. In wet manufacturing methods, Y / Z can be controlled by adjusting the hydrolysis and condensation conditions during the reaction (reaction temperature, reaction time, and stirring time), pH, the type of catalyst, and even the ratio of added monomers. For example, increasing Y / Z can be achieved by increasing the mixing ratio of bifunctional silane, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the pH of the solution, or lowering the temperature during hydrolysis. To decrease Y / Z, increasing the mixing ratio of tetrafunctional silane, increasing the temperature during the condensation reaction, lengthening the stirring time, increasing the pH of the solution, or increasing the temperature during hydrolysis.

[0037] To increase Y / X, methods include increasing the amount of oil treated, lengthening the treatment time, and raising the treatment temperature after increasing Y / Z. To decrease Y / X, methods include decreasing the amount of oil treated, shortening the treatment time, and lowering the treatment temperature after decreasing Y / Z.

[0038] The oil used in the external toner additive of the present invention is preferably silicone oil. Examples of silicone oils include dimethylsilicone oil, methylphenylsilicone oil, α-methylstyrene-modified silicone oil, and alkyl-modified silicone oils such as octyl-modified silicone oil. Because the external toner additive of the present invention is an organosilicon polymer, it is compatible with silicone oils of similar structure when treated with the silicone oil, and can retain the oil. This allows a larger amount of oil to be retained in the pores, resulting in excellent separation effects. Furthermore, the oil is retained inside and does not ooze out except during the fixing process, where pressure is applied, so development is not hindered. Furthermore, when organosilicon polymer particles are used as an external additive, there is a unique issue of the external additive becoming charged up due to durability. However, treatment with silicone oil facilitates the release of charge, thereby suppressing charge up.

[0039] The kinematic viscosity of the oil is 10mm 2 / s or more 5000mm 2 When the kinematic viscosity of the oil is within the above range, the oil is held in the pores when no pressure is applied, and only when pressure is applied in the fixing process does the oil seep out to the image surface in response to the pressure, achieving a separation effect. 2 / s or more 1000mm 2 From the above viewpoint, it is more preferable that the saturation rate is 1 / s or less.

[0040] The total pore volume of the pores in the external toner additive of the present invention is 0.30 cm 3 / g or more 1.00cm 3 / g or less. Specifically, it refers to the total pore volume of fine particles measured by the BJH method when the pore diameter of the pores is in the range of 1.7 nm to 300.0 nm. When the total pore volume is within the above range, an amount of oil effective for separation can be introduced into the pores. The total pore volume is 0.35 cm 3 / g or more 0.60cm 3 From the above viewpoint, it is more preferable that the saturation coefficient is 1 / g or less.

[0041] In wet production methods, the total pore volume of an external toner additive can be controlled by the hydrolysis and condensation conditions during the reaction (reaction temperature, reaction time, stirring time), pH, type of catalyst, and the ratio of added monomers. For example, methods for increasing the pore volume include increasing the mixing ratio of bifunctional silane, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the pH of the solution, and lowering the temperature during hydrolysis. Methods for decreasing the pore volume include increasing the mixing ratio of tetrafunctional silane, increasing the temperature during the condensation reaction, lengthening the stirring time, increasing the pH of the solution, and increasing the temperature during hydrolysis.

[0042] The volume average diameter of the pores of the external toner additive of the present invention is preferably 5 nm or more and 20 nm or less. When the average diameter of the pores is within this range, even oils with a certain degree of viscosity can be introduced into the pores, and further, when pressure is applied in the fixing process, the oil in the pores easily seeps out to the surface, thereby achieving a separation effect. From the above viewpoint, the average diameter of the pores is more preferably 8 nm or more and 5 nm or less.

[0043] In wet production methods, the average pore size of external toner additives can be controlled by the hydrolysis and condensation conditions during the reaction (reaction temperature, reaction time, stirring time), pH, type of catalyst, and the ratio of added monomers. For example, methods for increasing the pore size include increasing the mixing ratio of bifunctional silane, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the pH of the solution, and lowering the temperature during hydrolysis. Methods for decreasing the pore size include increasing the mixing ratio of tetrafunctional silane, increasing the temperature during the condensation reaction, lengthening the stirring time, increasing the pH of the solution, and increasing the temperature during hydrolysis.

[0044] The method for measuring the abundance ratio of the components of the organosilicon polymer particles will be described in detail below. 29In 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 particles. The structure bonded to Si can be identified by identifying the position of each peak using a standard sample. Furthermore, the abundance ratio of each constituent compound can be calculated from the peak area obtained. The ratio of the peak area of ​​the M unit structure (Chemical Formula 1), D unit structure (Chemical Formula 2), T unit structure (Chemical Formula 3), and Q unit structure (Chemical Formula 4) to the total peak area attributed to the silicon polymer can be calculated.

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka] (Ra, Rb, Rc, Rd, Re, and Rf each represent an alkyl group having 1 to 6 carbon atoms.)

[0049] The external toner additive of the present invention is 29 In a chart obtained by Si-NMR measurement, when the total peak area derived from the silicon polymer is SA and the peak area derived from the D unit is S2, it is preferable to satisfy 0.20≦S2 / SA≦0.70. Within this range, the pore diameter and pore volume are optimized, making it easy to achieve separation effects without impairing developability. Furthermore, when silicone oil is used as the oil, since the silicone oil also contains a D unit structure, it is well-compatible and easily supported in the pores. Furthermore, a charge-up suppression effect is also obtained. From the above perspectives, it is more preferable that 0.50≦S2 / SA≦0.70.

[0050] The external toner additive of the present invention is 29 In the chart obtained by Si-NMR measurement, when the total peak area derived from the silicon polymer is SA, the peak area derived from the Q unit is S4, and the peak area derived from the T unit is S3, 0.20≦S4 / SA≦0.60, 0.00≦S3 / SA≦0.50 It is preferable to satisfy the relationship. Within the above ranges, the pore diameter and pore volume become optimal, and it is easy to obtain a separation effect without impairing developability. From the above viewpoint, it is more preferable that 0.30≦S4 / SA≦0.50 and 0≦S3 / SA≦0.20.

[0051] The external toner additive of the present invention preferably has a compression cohesion value of 20 mJ to 70 mJ at 30 kPa and a compression cohesion value of 120 mJ to 180 mJ at 60 kPa. The compression cohesion value represents the degree of particle cohesion after compressing the particles under a predetermined pressure. It is believed that when oil is introduced into the pores, the more pressure is applied, the more oil seeps out, resulting in a higher cohesion value. When the compression cohesion value at 30 kPa is within the above range, the oil does not seep out when no significant pressure is applied, and remains in the pores, preventing contamination and impairing developability. When the compression cohesion value at 60 kPa is within the above range, the oil seeps out when pressure is applied, resulting in a separation effect. From the above perspective, it is more preferable that the compression cohesion value at 30 kPa is 30 mJ to 60 mJ, and that the compression cohesion value at 60 kPa is 140 mJ to 170 mJ.

[0052] The compression cohesion of the external toner additive can be controlled by the pore volume, pore diameter and oil treatment amount. The methods for controlling the pore volume and pore diameter are as described above.

[0053] The content of the external toner additive of the present invention relative to toner particles (toner base particles) is preferably 0.1 to 20.0 parts by weight per 100 parts by weight of toner particles. Within this range, charge-up can be sufficiently suppressed by the internal silicone oil, and a sufficient amount of oil seeps out onto the image surface during fixing, resulting in a separation effect. From the above perspectives, the content is more preferably 0.5 to 15.0 parts by weight. Even more preferably, it is 1.0 to 10.0 parts by weight.

[0054] The adhesion rate of the external toner additive of the present invention to the toner base particles is preferably 50% or more, more preferably 70% or more, based on the mass of the toner. When the adhesion rate is within the above range, a sufficient amount of the external toner additive is present on the transferred image during fixing, thereby achieving a separation effect. The adhesion rate of the external toner additive to the toner base particles can be controlled by the toner manufacturing method. For example, a method in which the external toner additive is mixed with the toner particles and then heat-treated can be mentioned (the heat-treatment method will be described in detail later).

[0055] [Toner particles] Next, the constitution of the toner particles to which the external toner additive of the present invention is externally added will be described.

[0056] <Binder 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] 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.

[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 Si-CH3 in the external additive interact with each other, further improving the toner charging property in a high-humidity environment. The acid value is more preferably 1 mgKOH / g or more and 20 mgKOH / g or less, and even more preferably 1 mgKOH / g or more and 15 mgKOH / g or less.

[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 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] An example of a dye for cyan toner is CI Solvent Blue 70.

[0065] 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. An example of a yellow toner dye is CI Solvent Yellow 162.

[0066] 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.

[0067] <Wax> The toner of the present invention may contain wax, if necessary. Examples of wax include the following.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] <Charge control agent> The toner of the present invention may contain a charge control agent as needed. Known charge control agents can be used as the charge control agent contained in the toner, but particularly preferred are metal compounds of aromatic carboxylic acids, which are colorless, can charge the toner quickly, and can stably maintain a constant charge amount.

[0072] 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.

[0073] The amount of the charge control agent added is preferably 0.2 parts by mass or more and 10.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0074] <Inorganic fine powder> In addition to the external toner additives described above, other inorganic fine powders may also be used in the toner of the present invention, if necessary. 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 powders are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0075] As an external additive to improve fluidity, 2 / g or more 400m 2 / g or less is preferred. In order to simultaneously improve fluidity and stabilize durability, inorganic fine particles having a specific surface area within the above range may be used in combination. The inorganic fine powder is preferably used in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of toner particles. When the above range is satisfied, the effect of charge stability is easily obtained.

[0076] <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 two-component developer contains a toner and a magnetic carrier, and that the toner is the toner of the present invention.

[0077] 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.

[0078] 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.

[0079] <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.

[0080] The toner can be obtained by mixing the external toner additive of the present invention, and, if necessary, the other external additives, with the obtained toner particles. The toner particles can be mixed with the external toner additive of the present invention 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).

[0081] Furthermore, in order to control the adhesion rate of the external toner additive to the toner particles, it is preferable to mix the external toner additive with the toner particles to obtain a toner particle mixture and then perform a heat treatment. For example, the heat treatment can be performed with hot air using a heat treatment device shown in FIG.

[0082] The heat treatment device has a treatment chamber 6 for heat-treating the toner particle mixture, a toner particle mixture supply means for supplying the toner particle mixture to the treatment chamber 6, a hot air supply means 7 for supplying hot air for heat-treating the toner particle mixture supplied from the toner particle mixture supply means, and a recovery means 10 for discharging the heat-treated toner particles outside the treatment chamber 6 from an outlet provided in the treatment chamber 6 and recovering them.

[0083] 1 further includes a regulating means 9 as a cylindrical member, and the processing chamber 6 has a cylindrical shape that covers the outer peripheral surface of the regulating means 9. The hot air supplying means 7 is provided at one end of the cylindrical shape of the processing chamber 6 so that the hot air flows while rotating inside the cylindrical processing chamber 6. The toner particle mixture supplying means is composed of a plurality of supply pipes 5 provided on the outer periphery of the processing chamber 6.

[0084] Furthermore, the discharge port provided in the treatment chamber 6 is provided on the outer periphery of the end of the treatment chamber 6 on the side opposite to the side where the hot air supply means 7 is provided, so as to be on an extension of the rotation direction of the toner particle mixture. Heat treatment using a heat treatment device having the above-mentioned configuration will be described below.

[0085] The toner particle mixture supplied by the raw material constant-quantity supply means 1 is introduced into an introduction pipe 3, which is installed vertically to the raw material constant-quantity supply means 1, by compressed gas adjusted by a compressed gas flow rate adjustment means 2. The mixture that passes through the introduction pipe is uniformly dispersed by a conical protruding member 4 provided in the center of the raw material constant-quantity supply means 1, and is then introduced into eight supply pipes 5 that radiate outward, and into a treatment chamber 6 where heat treatment is carried out.

[0086] At this time, the flow of the mixture supplied to the processing chamber 6 is regulated by a regulating means 9 for regulating the flow of the mixture, which is provided in the processing chamber 6. Therefore, the mixture supplied to the processing chamber is heat-treated while swirling inside the processing chamber 6, and then cooled.

[0087] Heat for heat-treating the supplied mixture is supplied from hot air supply means 7, distributed by distribution member 12, and introduced into treatment chamber 6 by swirling member 13 for swirling the hot air in a spiral shape. The swirling member 13 for swirling the hot air has multiple blades, and the swirling of the hot air can be controlled by the number and angle of the blades. Hot air is supplied from hot air supply means outlet 11.

[0088] The heat-treated toner particles are cooled by cold air supplied from the cold air supplying means 8 (cold air supplying means 8-1, 8-2 and 8-3).

[0089] Next, the cooled toner particles are collected as toner by the collecting means 10 at the bottom end of the processing chamber. A blower (not shown) is provided ahead of the collecting means, and the toner particles are sucked and transported by the blower.

[0090] The powder particle supply port 14 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are the same, and the recovery means 10 of the thermal sphering treatment device is provided on the outer periphery of the treatment chamber so as to maintain the swirling direction of the swirled powder particles. Furthermore, the cold air supplied from the cold air supply means 8 is configured to be supplied from the outer periphery of the device to the circumferential surface inside the treatment chamber in a horizontal and tangential direction.

[0091] <Image forming device> When the toner of the present invention is used, an image forming apparatus is used which includes a support, an electrophotographic photosensitive member having a photosensitive layer formed on the support, an image forming means for forming an electrostatic image on the electrophotographic photosensitive member, a developing means for supplying toner to the electrostatic image formed on the electrophotographic photosensitive member, a transfer means for transferring the toner image from the electrophotographic photosensitive member to a recording medium, and a fixing means for fixing the toner image transferred onto the recording medium to the recording medium by heat and pressure.

[0092] [Methods for measuring various physical properties] The methods for measuring various physical properties are explained below.

[0093] <Separation of external toner additives and toner particles from toner> Physical properties can also be measured using external toner additives separated from toner using the following method. 200 g of sucrose (Kishida Chemical) is added to 100 mL of ion-exchanged water and dissolved over a hot water bath to prepare a sucrose concentrate. 31 g of the sucrose concentrate and 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a centrifuge tube to prepare a dispersion. 1 g of toner is added to this dispersion, and any clumps of toner are broken up using a spatula or similar tool.

[0094] The centrifuge tube is shaken in the shaker at 350 reciprocations per minute for 20 minutes. After shaking, the solution is transferred to a 50 mL glass tube for a swing rotor and centrifuged in a centrifuge at 3500 rpm for 30 minutes. After centrifugation, the toner is present in the top layer of the glass tube, and the external toner additive is present in the aqueous solution below. The aqueous solution below is sampled and centrifuged to separate the sucrose and the external toner additive, and the external toner additive is collected. Centrifugation is repeated as necessary to thoroughly separate the dispersion, after which the dispersion is dried and the external toner additive is collected.

[0095] When a plurality of external toner additives are added, the external toner additive of the present invention can be selected by utilizing a centrifugal separation method or the like.

[0096] <Method for measuring the number average particle size of primary particles of external toner additives> The number-average particle size of the primary particles of the external toner 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 a 5% Triton solution and 19.8 g of RO water were added to prepare a solution. Next, the tip of the probe 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.

[0097] <Separation of oil from external toner additives> The external toner additive is dissolved in toluene, ultrasonically dispersed for 60 minutes, and then centrifuged at 3700 rpm for 60 minutes. The particles that have settled to the bottom are left behind, and the hexane is transferred to a separate container. Fresh hexane is added, and the mixture is ultrasonically dispersed for 30 minutes, followed by centrifugation at 3700 rpm for 30 minutes. The hexane is transferred to a separate container, and the remaining particles are dried to obtain the external toner additive from which the oil component has been removed. The hexane transferred to a separate container can also be separated from the oil by vacuum distillation, and the mass of the resulting oil can be measured to determine the content of the external toner additive.

[0098] <Measurement of BET specific surface area of ​​external toner additives> The BET specific surface area S can be determined by a low-temperature gas adsorption method using a dynamic constant pressure method in accordance with the BET method (preferably the BET multipoint method). For example, a specific surface area measuring device (trade name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation) is used to adsorb nitrogen gas onto the surface of a sample, and measurement is performed using the BET multipoint method to determine the BET specific surface area Y (m 2 / g) can be calculated.

[0099] In addition, the theoretical BET specific surface area X (m 2 / g) is calculated by the following formula, assuming that the external toner additive is a perfect sphere. Theoretical BET specific surface area X = (4 × π × average equivalent circular diameter A2) / (4 / 3 × π × average equivalent circular diameter A3 / density) × 1000

[0100] Density (cm) required for calculation 3 The value of true density measured using a dry density meter Accupyc 1330 (manufactured by Shimadzu Corporation) is used as the value of the density (density).

[0101] <Measurement of Average Pore Diameter and Pore Volume of External Toner Additives> The average pore size and total pore volume of the external toner additive are measured by a gas adsorption method in which nitrogen gas is adsorbed onto the surface of a sample using a pore distribution analyzer Tristar 3000 (manufactured by Shimadzu Corporation). The measurement method follows the operating manual issued by Shimadzu Corporation.

[0102] First, approximately 0.5 g of sample is placed in a sample tube and vacuumed at 100°C for 24 hours. After vacuuming, the sample mass is precisely weighed to obtain a sample. From the obtained sample, the average pore size and total pore volume in the pore size range of 1.7 nm to 300.0 nm can be determined by the BJH method using the pore size distribution measurement device described above. The density value required for measurement is the true density value measured using a dry density meter, Accupyc 1330 (Shimadzu Corporation).

[0103] <Solid 29 Method for measuring the abundance ratio of constituent compounds in external toner additives using Si-NMR> solid 29In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional group that bonds to Si in the constituent compounds of the toner additive. By identifying the position of each peak using a standard sample, the structure that bonds 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 Q unit structure, T unit structure, and D unit structure to the total peak area can be calculated.

[0104] 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

[0105] After the measurement, the peaks of the multiple silane components of the sample having different substituents and bonding groups are separated into the following M unit structure, D unit structure, T unit structure, and Q unit structure by curve fitting, and the peak area of ​​each is calculated. M unit structure: (Ra)(Rb)(Rc)SiO 1 / 2 (S1) D unit structure: (Rd)(Re)Si(O 1 / 2 )2(S2) T unit structure: RfSi(O 1 / 2 )3(S3) Q unit structure: Si(O 1 / 2 )4(S4) Let (S1+S2+S3+S4)=SA.

[0106] In the formulas (S1), (S2), and (S3), Ra, Rb, Rc, Rd, Re, and Rf represent silicon-bonded organic groups such as hydrocarbon groups having 1 to 6 carbon atoms (e.g., alkyl groups), and halogen atoms. If the structure needs to be confirmed in more detail, please refer to the results of Si-NMR measurements. 13 C-NMR and 1 The results of H-NMR may also be used for identification. S2 / SA, S3 / SA, and S4 / SA are calculated from SA, S2, S3, and S4 thus determined.

[0107] <Measurement of Compression Cohesion of External Toner Additives> The compression cohesion of external toner additives is measured using a powder rheometer (FT4, Freeman Technology). First, 10 g of external toner additive is weighed into a dedicated cylindrical split container, and the external toner additive is compressed at the specified pressure (30 kPa, 60 kPa) using a compression test piston attached to the main body. The compressed external additive layer is leveled off in the split part of the measurement container, and the upper part of the powder layer is removed. Next, a dedicated needle-shaped tool is attached to the main body and penetrates vertically into the powder layer. The compression cohesion can be obtained by measuring the penetration force at this time.

[0108] <Method for measuring the adhesion rate of external toner additives to toner particles using the water washing method> (Water washing process) A 30 mL glass vial was filled with 20.7 g of sucrose (Kishida Chemical Co., Ltd.) dissolved in 10.3 g of ion-exchanged water and 6 mL of the surfactant Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) and mixed thoroughly to prepare a dispersion. The glass vial used was, for example, a VCV-30 (Nichiden Rika Glass Co., Ltd.) with an outer diameter of 35 mm and a height of 70 mm. 1.0 g of toner was added to the dispersion and allowed to settle naturally to prepare a pre-treatment dispersion. This pre-treatment dispersion was then shaken at 200 rpm for 5 minutes in a shaker (YS-8D model, Yayoi Corporation) to remove loosely adhered particles (external toner additives) from the toner particle surface. A centrifuge was used to separate the toner with the remaining tightly adhered particles from the detached particles. The centrifugal separation step was carried out at 3700 rpm for 30 minutes. The toner containing remaining fine particles was collected by suction filtration, dried, and washed with water to obtain the toner.

[0109] (Method for measuring the adhesion rate of fine particles) The method for measuring the adhesion rate of fine particles is shown below as an example. First, the amount of fine particles contained in the toner particles before the water washing process is quantified. This is done by measuring the Si element intensity in the toner particles using a wavelength dispersive X-ray fluorescence analyzer, Axios Advanced (manufactured by PANalytical). Next, the Si element intensity in the toner particles after the water washing process is measured in the same way. The adhesion rate (%) is calculated as follows: It is determined by (Si element intensity in toner particles after water washing treatment / Si element intensity in toner particles before water washing treatment)×100. [Example]

[0110] 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.

[0111] <Production Example of Toner Additive 1> 1. Hydrolysis process 43.2 g of RO water and 0.008 g of acetic acid as a catalyst were placed in a 200 ml beaker and stirred at 45° C. 27.2 g of tetraethoxysilane and 27.2 g of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours to obtain a raw material solution.

[0112] 2. Polycondensation process An alkaline aqueous medium was prepared by adding 68.8 g of RO water, 340.0 g of methanol, and 2.0 g of 28% aqueous ammonia to a 1000 ml beaker and stirring at 30°C. The raw material solution obtained in the hydrolysis step was added dropwise to this alkaline aqueous medium over 1 minute. The mixture after the dropwise addition of the raw material solution was stirred for 1.0 hour while maintaining the temperature at 30°C, allowing the polycondensation reaction to proceed and obtaining a polycondensation reaction liquid.

[0113] 3.Particleization process 1000g of RO water was placed in a 2000ml beaker, and the polycondensation reaction liquid obtained in the above polycondensation step was added dropwise over 10 minutes while stirring at 25°C. The mixture was heated to 40°C and stirred for 1.0 hour while maintaining the temperature at 40°C, yielding a dispersion containing silicon polymer particles having siloxane bonds.

[0114] 4. Filtration process The dispersion containing the silicon polymer particles having siloxane bonds obtained in the above-mentioned particulation step was stirred for 2.5 hours at 60°C. After leaving it 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 fine particles.

[0115] 5.Oil treatment process 10 g of the fine particles obtained in the above filtration process and 100 g of toluene were added to a 100 ml beaker and dispersed. 2 1 g of silicone oil at 1 / s was added and stirred at 60°C for 2 hours. The dispersion was distilled under reduced pressure to remove the solvent, and then dried at 50°C for 24 hours to obtain external toner additive 1. The number average particle size of the primary particles of external toner additive 1 was 0.12 μm. The physical properties of external toner additive 1 are shown in Table 1. In Table 1, the "oil content (parts by mass)" indicates the amount of oil per 100 parts by mass of the microparticles (organosilicon polymer particles).

[0116] <Production Example of Toner Additive 2> Except for changing the amount of silicone oil used in the oil treatment step to 0.6 g, the same procedure as in the production example for external toner additive 1 was carried out to obtain external toner additive 2. The physical properties of the obtained external toner additive 2 are shown in Table 1.

[0117] <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 2, except that in the condensation polymerization step, the stirring temperature of the mixed solution after dropwise addition of the raw material solution was changed to 25°C and the stirring time was changed to 0.5 hours. The physical properties of the obtained external toner additive 3 are shown in Table 1.

[0118] <Production Example of Toner Additive 4> External toner additive 4 was obtained in the same manner as in the production example for external toner additive 1, except that in the hydrolysis step, the amounts of tetraethoxysilane, trimethoxymethylsilane, and dimethyldimethoxysilane were changed to 22.3 g, 9.7 g, and 21.5 g, respectively, and the amount of silicone oil used in the oil treatment step was changed to 1.5 g. The physical properties of the obtained external toner additive 4 are shown in Table 1.

[0119] <Production Example of Toner Additive 5> Except for changing the amount of silicone oil used in the oil treatment step to 1.8 g, the same procedure as in the production example for external toner additive 4 was carried out to obtain external toner additive 5. The physical properties of the obtained external toner additive 5 are shown in Table 1.

[0120] <Production Example of Toner Additive 6> External toner additive 6 was obtained in the same manner as in the production example for external toner additive 1, except that in the hydrolysis step, tetraethoxysilane was changed to 22.3 g, trimethoxymethylsilane to 24.3 g, and dimethyldimethoxysilane to 8.6 g. The physical properties of the obtained external toner additive 6 are shown in Table 1.

[0121] <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 hydrolysis step, tetraethoxysilane was changed to 44.6 g and dimethyldimethoxysilane was changed to 17.2 g. The physical properties of the obtained external toner additive 7 are shown in Table 1.

[0122] <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 hydrolysis step, tetraethoxysilane was changed to 59.5 g and dimethyldimethoxysilane was changed to 8.6 g. The physical properties of the obtained external toner additive 8 are shown in Table 1.

[0123] <Production Example of Toner Additive 9> In the hydrolysis step, the amount of tetraethoxysilane was changed to 63.2 g and the amount of dimethyldimethoxysilane was changed to 6.4 g, and the same procedure as in the production example for external toner additive 1 was repeated to obtain external toner additive 9. The physical properties of the obtained external toner additive 9 are shown in Table 1.

[0124] <Production Example of Toner Additive 10> External toner additive 10 was obtained in the same manner as in the production example for external toner additive 1, except that in the hydrolysis step, tetraethoxysilane was changed to 22.3 g, dimethyldimethoxysilane was changed to 30.0 g, and in the condensation polymerization step, 28% aqueous ammonia was changed to 1.5 g. The physical properties of the obtained external toner additive 10 are shown in Table 1.

[0125] <Production Example of Toner Additive 11> In the hydrolysis step, the amount of tetraethoxysilane was changed to 68.4 g and the amount of dimethyldimethoxysilane was changed to 3.4 g, and the same procedure as in the production example for external toner additive 1 was carried out to obtain external toner additive 11. The physical properties of the obtained external toner additive 11 are shown in Table 1.

[0126] <Production Example of Toner Additive 12> In the hydrolysis step, the amount of tetraethoxysilane was changed to 14.9 g and the amount of dimethyldimethoxysilane was changed to 34.3 g, and the same procedure as in the production example for external toner additive 1 was carried out to obtain external toner additive 12. The physical properties of the obtained external toner additive 12 are shown in Table 1.

[0127] <Production Example of Toner Additive 13> Except for changing the amount of 28% aqueous ammonia in the polycondensation step to 2.5 g, the same procedure as in the production example for external toner additive 11 was carried out to obtain external toner additive 13. The physical properties of the obtained external toner additive 13 are shown in Table 1.

[0128] <Production Example of Toner Additive 14> External toner additive 14 was obtained in the same manner as in the production example for external toner additive 10, except that the stirring temperature in the condensation polymerization step was changed to 25° C. The physical properties of the obtained external toner additive 14 are shown in Table 1.

[0129] <Production Example of Toner Additive 15> The viscosity of the silicone oil used in the oil treatment process is 10 mm. 2 With the exception of changing the amount of the additive to be used to produce the external toner additive 1, the procedure was the same as in the production example for the external toner additive 1, and an external toner additive 15 was obtained. The physical properties of the external toner additive 15 obtained are shown in Table 1.

[0130] <Production Example of Toner Additive 16> The viscosity of the silicone oil used in the oil treatment process is 5000mm 2 / s, the same procedure as in the production example of external toner additive 1 was repeated to obtain external toner additive 16. The physical properties of the obtained external toner additive 16 are shown in Table 1.

[0131] <Production Example of Toner Additive 17> The viscosity of the silicone oil used in the oil treatment process is 10,000mm 2 / s, the same procedure as in the production example of external toner additive 1 was carried out to obtain external toner additive 17. The physical properties of the obtained external toner additive 17 are shown in Table 1.

[0132] <Production Example of Toner Additive 18> Except for changing the oil used in the oil treatment step to paraffin oil, the same procedure as in the production example of external toner additive 1 was carried out to obtain external toner additive 18. The physical properties of the obtained external toner additive 18 are shown in Table 1.

[0133] <Production Example of Toner Additive 19> Except for changing the oil used in the oil treatment step to fluorine oil, the same procedure as in the production example of external toner additive 1 was carried out to obtain external toner additive 19. The physical properties of the obtained external toner additive 19 are shown in Table 1.

[0134] <Production Example of Toner Additive 20> External toner additive 20 was obtained in the same manner as in the production example for external toner additive 1, except that in the hydrolysis step, tetraethoxysilane and dimethyldimethoxysilane were not added, but 48.6 g of trimethoxymethylsilane was added instead, and the stirring temperature was changed to 30°C and the stirring time to 0.5 hours. The physical properties of the obtained external toner additive 20 are shown in Table 1.

[0135] <Production Example of Toner Additive 21> External toner additive 21 was obtained in the same manner as in the production example for external toner additive 1, except that in the hydrolysis step, the amount of acetic acid added was changed to 0.01 g, the stirring time was changed to 2.0 hours, the stirring temperature was changed to 50°C, and further the stirring time in the polycondensation step was changed to 1.5 hours. The physical properties of the obtained external toner additive 21 are shown in Table 1.

[0136] <Production Example of Toner Additive 22> Except for changing the amount of 28% aqueous ammonia used in the polycondensation step to 2.5 g and further changing the dropping time of the polycondensation reaction liquid to 5 minutes in the particulate formation step, the same procedure as in the production example for external toner additive 1 was carried out to obtain external toner additive 22. The physical properties of the obtained external toner additive 22 are shown in Table 1.

[0137] <Production Example of Toner Additive 23> A 2000 ml beaker was charged with 124.0 g of ethanol, 24.0 g of RO water, and 10.0 g of 28% aqueous ammonia. The solution was adjusted to 70°C, and 232.0 g of tetraethoxysilane and 84.0 g of 5.4% aqueous ammonia were added dropwise over 0.5 hours with stirring. After the addition was complete, stirring was continued for another 0.5 hours to allow hydrolysis to occur, yielding a dispersion of silicon polymer particles having siloxane bonds.

[0138] To the dispersion of silicon polymer particles having siloxane bonds obtained in the above step, 150.0 g of hexamethyldisilazane was added at room temperature, and the dispersion was then heated to 50-60°C and stirred for 3.0 hours. The powder in the dispersion was recovered by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain fine particles. The obtained fine particles were treated with oil in the same manner as for external toner additive 1 to obtain external toner additive 23. The physical properties of the obtained external toner additive 23 are shown in Table 1.

[0139] <Production example of external toner additive 24> Except for not carrying out the oil treatment step, the same procedure as in the production example of external toner additive 23 was carried out to obtain external toner additive 24. The physical properties of the obtained external toner additive 24 are shown in Table 1.

[0140] <Production example of external toner additive 25> A catalyst solution was obtained by adding 500 parts of methanol and 70 parts of water adjusted to pH 7.2 with 10% by mass aqueous ammonia to a 1.5 L glass reaction vessel equipped with a stirrer, a dropping nozzle, and a thermometer. After adjusting this alkaline catalyst solution to 30°C, 100 parts of tetramethoxysilane, 20 parts of dimethylformamide, and 20 parts of 1.0% by mass aqueous ammonia were simultaneously added dropwise over 60 minutes with stirring to obtain a hydrophilic silica particle dispersion.

[0141] The obtained particle dispersion was filtered and oil-treated in the same manner as in the case of external toner additive 1 to obtain external toner additive 25. The physical properties of the obtained external toner additive 25 are shown in Table 1.

[0142] <Production Example of Toner Additive 26> A reactor equipped with a stirring blade was charged with 125 mL of a toluene solution of polyoxyethylene sorbitan trioleate (polyoxyethylene sorbitan trioleate concentration: 30 g / L) and 125 mL of an aqueous solution of sodium silicate in ion-exchanged water (SiO2 concentration: 6.5 mol / L), and the contents of the vessel were stirred to obtain a W / O emulsion. Next, 500 mL of an aqueous ammonium carbonate solution (ammonium carbonate concentration: 1.5 mol / L) was added to 250 mL of the resulting W / O emulsion. The resulting mixture was stirred at a rotation speed (stirring speed) of 300 rpm for 30 minutes to obtain a suspension. The solids were then filtered from the resulting suspension, and the filtered solids were dried at 45°C for 48 hours to obtain a silica particle powder.

[0143] The obtained powder of silica particles was treated with oil in the same manner as in the case of external toner additive 1 to obtain external toner additive 26. The physical properties of the obtained external toner additive 26 are shown in Table 1.

[0144] <Production example of external toner additive 27> External toner additive 27 was obtained in the same manner as in the production example for external toner additive 11, except that the amount of 28% ammonia water in the condensation polymerization step was changed to 3.0 g, the reaction temperature was changed to 40°C, and the stirring time was changed to 2.0 hours. The physical properties of the obtained external toner additive 27 are shown in Table 1.

[0145] <Production Example of Toner Additive 28> Except for not carrying out the oil treatment step, the same procedure as in the production example of external toner additive 1 was carried out to obtain external toner additive 28. The physical properties of the obtained external toner additive 28 are shown in Table 1.

[0146] <Production Example of Toner Additive 29> External toner additive 29 was obtained in the same manner as in the production example for external toner additive 1, except that the amount of 28% ammonia water used in the polycondensation step was changed to 2.5 g and the dropping time of the polycondensation reaction liquid in the particulate formation step was changed to 1 minute. The physical properties of the obtained external toner additive 29 are shown in Table 1.

[0147] <Production Example of Toner Additive 30> External toner additive 30 was obtained in the same manner as in the production example for external toner additive 1, except that in the hydrolysis step, the amount of acetic acid added was changed to 0.02 g, the stirring time was changed to 2.0 hours, the stirring temperature was changed to 50°C, and further the stirring time in the condensation polymerization step was changed to 2.0 hours. The physical properties of the obtained external toner additive 30 are shown in Table 1.

[0148] <Production Example of Toner Additive 31> Except for changing the amount of silicone oil used in the oil treatment step to 3.0 g, the same procedure as in the production example for external toner additive 1 was carried out to obtain external toner additive 31. The physical properties of the obtained external toner additive 31 are shown in Table 1.

[0149] [Table 1]

[0150] <Production Example of Polyester Resin A1> 76.9 parts (0.167 moles) of polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane Terephthalic acid (TPA) 25.0 parts (0.145 moles) Adipic acid 8.0 parts (0.054 moles) 0.5 parts titanium tetrabutoxide 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.

[0151] <Production Example of Polyester Resin A2> 71.3 parts (0.155 moles) of polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 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, yielding polyester resin A2. The acid value of this polyester resin A2 was 10 mgKOH / g.

[0152] <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.

[0153] <Toner 1 manufacturing example> 100 parts of toner particles 6.0 parts of external additive particles for toner 1 The above materials were mixed in a Henschel mixer FM-10C (Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 30 s -1 The mixture was mixed for a rotation time of 10 minutes to obtain toner particle mixture 1.

[0154] (Heat treatment process) The obtained toner particle mixture 1 was subjected to heat treatment using the surface treatment device shown in FIG. 1 to obtain toner 1. The physical properties of toner 1 are shown in Table 2. The operating conditions for the heat treatment were a feed rate of 2 kg / hr, a hot air temperature of 150°C, and a hot air flow rate of 6 m 3 / min., cold air temperature = -5℃, cold air flow rate = 2.5m 3 / min., Blower air volume = 11m 3 / min., injection air flow rate = 1m 3 / min.

[0155] <Production examples of toners 2 to 37> Toners 2 to 37 were obtained in the same manner as in the production example of Toner 1, except that the toner particles, toner external additives, whether or not a hot air treatment step was performed, and the hot air temperature in the heat treatment step were changed to those shown in Table 2. The physical properties of Toners 2 to 37 are shown in Table 2.

[0156] [Table 2]

[0157] <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 Number average particle size: 0.50 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite 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.

[0158] 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: 58% by mass Magnetite treated with the above silane compound: 26% by mass The above materials, 5 parts of a 28% by weight aqueous ammonia solution, and 20 parts of water were placed in a flask, and the temperature was raised to 85°C over 30 minutes while stirring and mixing, and the temperature was maintained at 85°C for 30 minutes. The polymerization reaction was carried out for 3 hours, and the resulting phenolic resin was cured. The cured phenolic resin was then cooled to 30°C, and more water was added. The supernatant was removed, and the precipitate was washed with water and air-dried. This was then dried at 60°C under reduced pressure (5 mmHg or less) to obtain magnetic material-dispersed spherical carrier 1. The volume-based 50% particle size (D50) was 34.2 μm.

[0159] <Manufacturing 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.

[0160] <Production examples of two-component developers 2 to 37> Two-component developers 2 to 37 were obtained by carrying out production in the same manner as in the production example of two-component developer 1, except that the toner was changed as shown in Table 3.

[0161] [Table 3]

[0162] Example 1 <Toner evaluation method> The image forming apparatus used was a modified Canon imagePRESS C810 digital commercial printing printer, with two-component developer 1 loaded into the cyan developer unit. The apparatus was modified so that the fixing temperature, process speed, developer carrier DC voltage VDC, electrostatic latent image carrier charging voltage VD, and laser power could be freely set. Image output evaluation was performed by outputting an FFh image (solid image) with the desired image ratio, and adjusting VDC, VD, and laser power so that the toner coverage on the FFh image on the paper was as desired, and then evaluating as described below.

[0163] FFh is a value that represents 256 gradations in hexadecimal, with 00h being the first gradation of the 256 gradations (white background) and FFh being the 256th gradation of the 256 gradations (solid area).

[0164] The evaluation was carried out based on the following evaluation methods, and the results are shown in Table 4.

[0165] [Fixation separation property (wrapping resistance)] ·Paper:CS-064(64.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.80mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: A 2cm x 20cm image placed on the long edge of the A4 paper with a 2mm margin from the leading edge of the paper. Test environment: High temperature and humidity: 30°C / 80%RH (hereinafter referred to as "H / H"). Fixing temperature: 140°C, increasing in 5°C increments Process speed: 400mm / sec

[0166] The evaluation image was output, and the winding resistance was evaluated at the highest fixing temperature at which winding did not occur according to the following criteria: Rank F or higher was deemed to be a level at which the effects of the present invention were obtained.

[0167] (Evaluation criteria) A: 170℃ or higher B: 165℃ or higher and lower than 170℃ C: 160℃ or higher but lower than 165℃ D: 155℃ or higher and lower than 160℃ E: 150℃ or higher but lower than 155℃ F: 145℃ or higher but lower than 150℃ G: Less than 145°C

[0168] [Developability] ·Paper: GF-C081(81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.45mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: 2mm wide strips of solid area and 18mm wide strips of white area are arranged repeatedly in a direction parallel to the paper feed direction of the A4 paper. Test environment: Normal temperature and low humidity (23°C / 5%RH)

[0169] When the pattern image had been output on 10,000 sheets, the output was temporarily stopped, and then an image in which the entire surface of the paper was halftone (80h) was output.

[0170] The image density of the entire solid image was measured at 20 random locations using an X-Rite color reflection densitometer ("500 Series," manufactured by X-Rite Corporation), and the image density was evaluated using the difference between the maximum and minimum values ​​of the image density (image density difference). If oil from the external toner additive transfers to the component and contaminates it, this can cause density changes. A rating of F or higher is considered to be a level at which the effects of the present invention are achieved.

[0171] (Evaluation criteria) A: Image density difference is less than 0.02 B: Image density difference is 0.02 or more and less than 0.04 C: Image density difference is 0.04 or more and less than 0.06 D: Image density difference is 0.06 or more and less than 0.08 E: Image density difference is 0.08 or more and less than 0.10 F: Image density difference is 0.10 or more and less than 0.12 G: Image density difference is 0.12 or more

[0172] [Charge-up property] The charge-up property was evaluated by measuring the change in image density. A Canon full-color copier, imagePress C800, was used as the image forming apparatus. The above-mentioned two-component developer was placed in the cyan developer of the image forming apparatus, and the above toner was placed in the cyan toner container, and the evaluation described below was carried out. The modification was to remove the mechanism for discharging the excess magnetic carrier from the developer. The evaluation paper was plain paper GF-C081 (A4, basis weight 81.4 g / m 2 (sold by Canon Marketing Japan Inc.) was used.

[0173] The amount of toner on the paper in a FFh image (solid image) is 0.45 mg / cm 2 The settings were adjusted so that the result was as follows: FFh is the hexadecimal representation of 256 gradations, with 00h being the first gradation of 256 gradations (white background) and FF being the 256th gradation of 256 gradations (solid area). First, an image output test of 1,000 sheets was conducted at an image ratio of 1%. During the continuous printing of 1,000 sheets, the sheets were printed under the same development and transfer conditions (without calibration) as the first sheet.

[0174] After that, an image output test of 1,000 sheets was conducted at an image ratio of 80%. During the continuous printing of 1,000 sheets, the sheets were printed under the same development and transfer conditions (without calibration) as the first sheet. The image density of the 1,000th sheet printed at an image ratio of 1% was taken as the initial density, and the density of the 1,000th image printed at an image ratio of 80% was measured and evaluated.

[0175] The above test was carried out in a normal temperature and low humidity environment (N / L; temperature 23°C, relative humidity 5%). Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), the initial density and the density of the 1,000th image printed at an image ratio of 80% were measured, and the difference Δ was used to rank the images according to the following criteria. A grade of C or higher was considered good.

[0176] (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

[0177] Examples 2 to 28 The two-component developers 2 to 28 were each evaluated in the same manner as in Example 1. The evaluation results of Examples 2 to 28 are shown in Table 4.

[0178] Comparative Examples 1 to 9 Two-component developers 29 to 37 were each evaluated in the same manner as in Example 1. The evaluation results of Comparative Examples 1 to 9 are shown in Table 4.

[0179] [Table 4] [Explanation of symbols]

[0180] 1. Means for supplying fixed quantity raw material, 2. Means for adjusting compressed gas flow rate, 3. Inlet pipe, 4. Projecting member, 5. Supply pipe, 6. Processing chamber, 7. Means for supplying hot air, 8. Means for supplying cold air, 9. Regulating means, 10. Recovery means, 11. Outlet for the means for supplying hot air, 12. Distributing member, 13. Swirling member, 14. Powder particle supply port

Claims

1. An external toner additive comprising pore-containing organosilicon polymer particles and oil, the organosilicon polymer particles contain 5.0 parts by weight or more and 20.0 parts by weight or less of oil per 100 parts by weight of the organosilicon polymer particles, the number average particle size of the primary particles of the external toner additive is 0.05 μm or more and 0.30 μm or less; The BET specific surface area of ​​the external toner additive is X (m 2 / g), and the BET specific surface area of ​​the washed external toner additive obtained by washing the external toner additive with hexane is Y (m 2 / g), and the theoretical BET specific surface area calculated from the particle size of the external toner additive after washing is Z (m 2 / g), An external toner additive, characterized by satisfying the following formulae (i) and (ii): (i) 1.8≦Y / X≦15.0 (ii) 3.0≦Y / Z≦9.0

2. 2. The external toner additive according to claim 1, wherein the oil is a silicone oil.

3. The kinematic viscosity of the oil is 10 mm 2 / s or more 5000mm 2 3. The external toner additive according to claim 1, wherein the viscosity is 1 / s or less.

4. After the washing, the total pore volume of the external toner additive is 0.30 cm 3 / g or more 1.00cm 3 4. The external toner additive according to claim 1, wherein the molecular weight of the external toner additive is 1 / g or less.

5. 5. The external toner additive according to claim 1, wherein the volume average diameter of the pores in the external toner additive after washing is 5 nm or more and 20 nm or less.

6. The external additive for toner 29 6. The external toner additive according to claim 1, wherein, in a chart obtained by Si-NMR measurement, when the total peak area attributed to the silicon polymer is defined as SA and the peak area attributed to the D unit structure is defined as S2, SA and S2 satisfy the following formula: 0.20≦S2 / SA≦0.70

7. The external additive for toner 29 In the chart obtained by Si-NMR measurement, when the peak area attributed to the Q unit structure is S4 and the peak area attributed to the T unit structure is S3, the SA, the S3 and the S4 are 0.20≦S4 / SA≦0.60 0.00≦S3 / SA≦0.50 The external toner additive according to claim 6, which satisfies the above formula:

8. The external toner additive is (i) the compression cohesion value at 30 kPa is 20 mJ or more and 70 mJ or less; (ii) The compression cohesion value at 60 kPa is 120 mJ or more and 180 mJ or less. The external toner additive according to any one of claims 1 to 7.

9. A toner having toner particles and an external toner additive, A toner, wherein the external toner additive is the external toner additive according to any one of claims 1 to 8.

10. 10. The toner according to claim 9, wherein the external toner additive is contained in an amount of 0.1 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

11. 11. The toner according to claim 9, wherein the adhesion rate of the external toner additive to the toner particles is 50% or more based on the mass of the toner.

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