External additive for toner and toner

Abstract

The present invention relates to an external additive for toner and toner. An external additive for toner including particles of a silicon polymer having a siloxane bond and a Si-O-C bond, wherein in an FT-IR spectrum of the external additive obtained by an ATR method, a maximum peak exists in a range of 1030 cm ‑1 to 1070 cm ‑1 , when an average intensity in a range of 1015 cm ‑1 to 1025 cm ‑1 is represented by A, and an average intensity in a range of 1085 cm ‑1 to 1095 cm ‑1 is represented by B, A and B satisfy the following formula (1): 0.55 ≤ A / B ≤ 1.50...(1).

Description

Technical Field

[0001] The present disclosure relates to an external additive for a toner and a toner used in an electrophotographic method using the external additive for a toner. Background Art

[0002] In recent years, with the widespread use of full-color electrophotographic copiers, there has been an increasing demand for electrophotographic toners that are suitable for high-speed printing and have a long service life. Silica is generally known as an external additive for toners. For example, Japanese Patent Application Publication No. 2007-099582 discloses an example in which highly hydrophobic spherical sol-gel silica fine particles are added to toner base particles to improve the toner's charge stability.

[0003] However, in environments where toner frequently contacts members such as a carrier and exerts stress, such as when outputting images with low print density for a long period of time or when outputting images in a high-temperature, high-humidity environment, silica particles become embedded in the surface of toner particles. As a result, the surface state of the toner significantly changes, and there is room for improvement in toner flow stability and charging stability.

[0004] On the other hand, WO 2015 / 107961 and Japanese Patent Application Publication No. 2018-004949 include examples in which polyalkylsilsesquioxane fine particles are added to toner base particles to improve the fluidity and charging stability of the toner.

[0005] Furthermore, WO 2013 / 063291 includes an example in which it is stated that adding metal oxide-polymer composite particles including metal oxide particles and a polymer matrix to toner particles exhibits an effect of suppressing embedding into toner base particles. Summary of the Invention

[0006] However, it was found that the technologies described in the above patent documents could not suppress changes in the fine particles of external additives and the surface of the colorant when outputting images with low print density for a long time in a high temperature and high humidity environment, and all of these technologies still had room for improvement in the charging stability, image density, and color stability of the colorant.

[0007] The present disclosure provides an external additive for toner that has durable stability and charging stability even in a high-temperature and high-humidity environment and can suppress density fluctuation regardless of image printing rate, and also provides a toner using the external additive for toner.

[0008] The present disclosure relates to an external additive for toner including particles of a silicon polymer having a siloxane bond and a Si-OC bond, wherein

[0009] In the FT-IR spectrum of the external additive obtained by the ATR method,

[0010] The maximum peak is at 1030 cm -1 to 1070cm -1 within the range,

[0011] When the spectrum is at 1015cm -1 Up to 1025cm -1 The average intensity within the range is represented by A, and the -1 to 1095cm -1 When the average intensity within the range is represented by B, A and B satisfy the following formula (1):

[0012] 0.55≤A / B≤1.50 ...(1).

[0013] The present disclosure can provide a toner external additive that exhibits durable stability and charging stability even in high-temperature and high-humidity environments and suppresses density fluctuations regardless of the image printing rate, and also provides a toner using the toner external additive. Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 is FT-IR spectrum;

[0015] Figure 2 is an FT-IR spectrum; and

[0016] Figure 3 FT-IR spectrum. DETAILED DESCRIPTION

[0017] In the present disclosure, unless otherwise specified, the expressions "from XX to YY" and "XX to YY" indicating a numerical range indicate a numerical range including the lower limit and the upper limit as endpoints. When describing a numerical range in stages, the upper and lower limits of each numerical range can be arbitrarily combined.

[0018] The present inventors believe that this effect is due to the following mechanism. Since silica particles, commonly used as an external additive for toners, are composed of siloxane bonds (Si—O—Si), they have a very high crosslink density and are hard. Therefore, when outputting images with low print density for a long time, since toner particles are softer than silica particles, frequent contact occurs between components such as a carrier and the silica particles on the toner surface, exerting stress and causing the silica particles to become embedded in the toner particle surfaces.

[0019] Furthermore, particles including a large number of Si—OC bonds, such as polyalkylsilsesquioxane particles, have a low crosslinking density and are soft, so when the toner is subjected to stress, the polyalkylsilsesquioxane particles themselves may be crushed or broken.

[0020] As a result of intensive studies by the present inventors, it was found that the above problems can be solved by optimizing the content ratio of siloxane bonds (Si—O—Si) and Si—OC bonds inside the external additive particles.

[0021] The present disclosure relates to an external additive for toner including particles of a silicon polymer having a siloxane bond and a Si-OC bond, wherein

[0022] In the FT-IR spectrum of the external additive obtained by the ATR method,

[0023] The maximum peak is at 1030 cm -1 to 1070cm -1 within the range,

[0024] When the spectrum is at 1015cm -1 Up to 1025cm -1 The average intensity within the range is represented by A, and the -1 to 1095cm -1 When the average intensity within the range is represented by B, A and B satisfy the following formula (1):

[0025] 0.55≤A / B≤1.50 ...(1).

[0026] The present inventors believe that the detailed mechanism is as follows.

[0027] In the FT-IR spectrum, at 1015 cm -1 Up to 1025cm -1 The peaks in the range represent the stretching vibration of Si-OC bonds, and the peak at 1085 cm -1 to 1095cm -1 The peak within the range represents the stretching vibration of the siloxane bond (Si-O-Si). Satisfying formula (1) means that the ratio of Si-OC bonds to siloxane bonds (Si-O-Si) within the external additive particles is approximately the same, and the crosslinking density within the external additive particles is optimal.

[0028] The crosslinking density within the external additive particles is strongly correlated with the particle hardness, and within the range of formula (1), the particles themselves have the function of relaxing externally applied stress. Specifically, the stress on the toner can be relaxed, and the particles themselves have high toughness, so that even when outputting low-density images for a long time, changes in the toner surface state can be suppressed, and charging stability can also be improved.

[0029] 0.55≤A / B≤1.50 ...(1)

[0030] When A / B exceeds 1.50, the number of Si-O-C bonds is much greater than the number of siloxane bonds (Si-O-Si), resulting in a low crosslinking density of the external additive particles and the particles themselves being easily crushed or broken. Furthermore, when A / B is less than 0.55, the number of Si-O-C bonds is much less than the number of siloxane bonds (Si-O-Si), resulting in a high crosslinking density of the external additive particles and the external additive particles being easily embedded in the toner particles.

[0031] Furthermore, it is preferable that 0.80≤A / B≤1.20. Within this range, the abundance ratio of Si-OC bonds and siloxane bonds (Si-O-Si) inside the external additive particles becomes optimal, which is preferable from the viewpoints of toner durability stability and charging stability.

[0032] The method for producing the toner external additive, which is a silicon polymer particle, is not particularly limited, but the particles are preferably formed through a hydrolysis and polycondensation reaction of a silicon compound (silane monomer) obtained by a sol-gel method. Specifically, the particles are preferably formed by polymerizing a mixture of a bifunctional silane having two siloxane bonds and a tetrafunctional silane having four siloxane bonds through a hydrolysis and polycondensation reaction. Silane monomers such as bifunctional silane and tetrafunctional silane will be described below.

[0033] That is, the silicon polymer is preferably a condensation polymer of at least one silicon compound selected from the group consisting of bifunctional silanes and at least one silicon compound selected from the group consisting of tetrafunctional silanes. The proportion of the bifunctional silane is preferably 50 mol% to 70 mol%, and more preferably 61 mol% to 65 mol%. The proportion of the tetrafunctional silane is preferably 30 mol% to 50 mol%, and more preferably 35 mol% to 39 mol%.

[0034] The present inventors have found that the above effects are exerted by adjusting the mixing ratio of monomers, the solvent temperature during hydrolysis and condensation reactions, the type of catalyst, the stirring time, the pH of the solution, and the like in the production method of the external additive for toner.

[0035] For example, A / B can be increased by increasing the mixing ratio of difunctional silane, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the pH of the solution, and lowering the temperature during the hydrolysis. A / B can be decreased by increasing the mixing ratio of tetrafunctional silane, increasing the temperature during the condensation reaction, extending the stirring time, increasing the pH of the solution, and increasing the temperature during the hydrolysis.

[0036] Furthermore, it is necessary that the maximum peak in the FT-IR spectrum of the external additive for toner obtained by the ATR method exists at 1030 cm -1 to 1070cm -1 The presence of the maximum peak in the above range means that the crosslinking density of Si-OC bonds and Si-O-Si bonds is high and a strong three-dimensional network is formed, and in this case, the resistance of the external additive to external stress is strong and deformation and crushing can be suppressed.

[0037] The maximum peak preferably exists at 1040 cm -1 to 1055cm -1 The position of the maximum peak can be controlled by the mixing ratio of the monomers.

[0038] The toner external additive includes particles of a silicon polymer having a siloxane bond. The silicon polymer particles preferably contain the silicon polymer in an amount of 90% by mass or more, and more preferably 95% by mass or more.

[0039] There is no particular limitation on the production method of the silicon polymer particles, and for example, the silicon polymer particles can be obtained by dropping a silane compound onto water to initiate a hydrolysis and condensation reaction mediated by a catalyst, followed by filtering and drying the obtained suspension. The particle size can be controlled based on, for example, the type of catalyst, the mixing ratio, the reaction start temperature, and the addition time. Examples of the catalyst include acidic catalysts such as hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, and alkaline catalysts such as ammonia water, sodium hydroxide, and potassium hydroxide, although not limited thereto.

[0040] The silicon polymer particles are preferably produced according to the following method. Specifically, the method preferably includes a first step of obtaining a hydrolyzate of a silicon compound; a second step of mixing the resulting hydrolyzate with an alkaline aqueous medium to initiate a polycondensation reaction of the hydrolyzate; and a third step of mixing the polycondensation reaction product with an aqueous solution to initiate particle formation. In some cases, the hydrophobized spherical silicon polymer particles can be obtained by further mixing a hydrophobizing agent into the dispersion of the spherical silicon polymer particles.

[0041] In the first step, the silicon compound and the catalyst are brought into contact with each other by methods such as stirring or mixing an aqueous solution in which an acidic or alkaline substance serving as a catalyst is dissolved in water. As the catalyst, known catalysts can preferably be used. Specifically, examples of suitable acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, and examples of suitable basic catalysts include ammoniacal liquor, sodium hydroxide, and potassium hydroxide.

[0042] The amount of the catalyst used can be appropriately adjusted according to the types of the silicon compound and the catalyst. Preferably, the amount of the catalyst used is in the range of 1×10 -3 The amount is selected within the range of parts by mass to 1 part by mass.

[0043] The amount of catalyst used was 1×10 -3 When the amount of water is 1 part by mass or more, the reaction proceeds sufficiently. On the other hand, when the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles becomes low, and hydrolysis becomes easier. The amount of water used is preferably 2 to 15 mol per 1 mol of the silicon compound. When the amount of water is 2 mol or more, the hydrolysis reaction proceeds sufficiently, and when the amount of water is 15 mol or less, productivity is improved.

[0044] The reaction temperature is not particularly limited, and the reaction can be carried out at room temperature or in a heated state, but it is preferred that the reaction be carried out in a state where the temperature is maintained at 10 to 60° C., since in this case, a hydrolysis product is obtained in a short time and a partial condensation reaction of the generated hydrolysis product can be suppressed. The reaction time is not particularly limited and can be appropriately selected in consideration of the reactivity of the silicon compound used, the composition of the reaction solution resulting from the preparation of the silicon compound, acid, and water, and productivity.

[0045] In the method for producing silicon polymer particles, the second step involves mixing the raw material solution obtained in the first step with an alkaline aqueous medium to initiate a polycondensation reaction of the particle precursor. This results in a polycondensation reaction solution. The alkaline aqueous medium is a solution obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0046] The alkaline component used in the alkaline aqueous medium exhibits alkalinity and serves 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.

[0047] The amount of the basic component used is an amount in which the basic component neutralizes the acid and effectively serves as a catalyst for the polycondensation reaction; in the case where ammonia is used as the basic component, for example, the amount of the basic component can be generally selected within the range of 0.01% by mass to 12.5% ​​by mass relative to 100 parts by mass of the mixture with water and the organic solvent.

[0048] In the second step, in addition to alkaline components and water, an organic solvent can be further used to prepare an alkaline aqueous medium. There is no particular restriction on the organic solvent as long as it is compatible with water, but herein preferably an organic solvent that dissolves 10g of water or more per 100g at normal temperature and pressure.

[0049] Specific examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, 2-propanol and butanol; polyols such as ethylene glycol, diethylene glycol, propylene glycol, glycerol, trimethylolpropane and hexanetriol; ethers such as ethylene glycol monoethyl ether, acetone, ethyl ether, tetrahydrofuran and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

[0050] Among the organic solvents listed above, alcohol solvents such as methanol, ethanol, 2-propanol or butanol are preferred. In the hydrolysis and dehydration condensation reactions, it is more preferred to select the same alcohol as the leaving alcohol as the organic solvent.

[0051] The third step involves mixing the polycondensation reaction product obtained in the second step with an aqueous solution to initiate the formation of particles. Water (tap water or pure water, etc.) can be suitably used as an aqueous solution in this article, but components such as salt, acid, alkali, organic solvent, surfactant or water-soluble polymer that are compatible with water can be further added to the water. The temperature of the polycondensation reaction solution and the temperature of the aqueous solution during mixing are not particularly limited, and herein, the scope of 5 to 70° C. is suitably selected considering the composition of the solution and productivity.

[0052] Known methods can be used, without particular limitation, to recover the silicone polymer particles. For example, the floating powder can be scooped out or filtered, but filtration is preferred due to its simplicity and convenience. There are no particular limitations on the filtration method, and known equipment such as vacuum filtration, centrifugal filtration, or pressure filtration can be selected. Filter paper, filters, or filter cloth used for filtration are not particularly limited, as long as they are industrially available and can be appropriately selected depending on the equipment used.

[0053] The hydrophobicity of the silicon polymer particles can be adjusted by treating the surface of the silicon polymer particles in a known manner, for example, using a silane coupling agent or silicone oil.

[0054] The monomer used can be appropriately selected based on compatibility with the solvent and catalyst, hydrolysis properties, etc. However, tetraethoxysilane is preferred as the tetrafunctional silane, and dimethyldimethoxysilane is preferred as the difunctional silane.

[0055] The silicon polymer is preferably a condensation polymer of at least one silicon compound selected from the group consisting of silicon compounds having a structure represented by the following formula (2).

[0056]

[0057] In formula (2), R 2 、R 3 、R 4 and R 5 R independently represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, and more preferably 1 or 2), a phenyl group, or a reactive group (e.g., a halogen atom, a hydroxyl group, an acetoxy group, or an alkoxy group (preferably having 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms)). 2 、R 3 、R 4 and R 5 At least one of the groups is a reactive group.

[0058] R 2 、R 3 、R 4 and R 5 It is preferably independently an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms, and more preferably 1 or 2 carbon atoms) or an alkoxy group (preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms).

[0059] In order to obtain silicon polymer particles, a silicon compound having four reactive groups in one molecule of formula (2) (tetrafunctional silane) can be used, wherein R in formula (2) is 2 is an alkyl group or a phenyl group and has three reactive groups (R 3 、R 4 、R 5 ) of an organosilicon compound (trifunctional silane), wherein R in formula (2) 2 and R 3 Each is an alkyl group or a phenyl group and has two reactive groups (R 4 、R 5 ) of an organosilicon compound (bifunctional silane), and wherein R 3 、R 4 、R 5 Each is an alkyl group or a phenyl group and has one reactive group (R 5 ) of an organosilicon compound (monofunctional silane).

[0060] These reactive groups are hydrolyzed, polyaddition-polymerized, and polycondensation-polymerized to form a cross-linked structure, and silicon polymer particles can be obtained. 3 、R 4 and R 5 The hydrolysis, polyaddition and polycondensation can be controlled by reaction temperature, reaction time, reaction solvent and pH.

[0061] The tetrafunctional silane can be exemplified by tetramethoxysilane, tetraethoxysilane, and tetraisocyanatosilane.

[0062] The trifunctional silane may be exemplified by methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxy Methoxyhydroxysilane, methyldiethoxyhydroxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0063] The bifunctional silane can be exemplified by di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethyldimethoxysilane, diethoxydimethylsilane, and diethyldimethoxysilane.

[0064] The monofunctional silane can be exemplified by tert-butyldimethylchlorosilane, tert-butyldimethylmethoxysilane, tert-butyldimethylethoxysilane, tert-butyldiphenylchlorosilane, tert-butyldiphenylmethoxysilane, tert-butyldiphenylethoxysilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, trimethylmethoxysilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, and triphenylethoxysilane.

[0065] The number average particle size of the primary particles of the toner external additive is preferably 0.02 μm to 0.30 μm. When the number average particle size of the primary particles is within this range, the toner particles are easily and uniformly coated with the external additive. Furthermore, since stress on the toner is suppressed, the effect of charge stability can be easily achieved.

[0066] When the number average particle size of the primary particles of the toner external additive is 0.02 μm or larger, stress on the toner is reduced, making it less likely that the external additive particles will become embedded in the toner particle surface, even when outputting a large number of low-density images for a long period of time in harsh environments such as high temperature and high humidity. Furthermore, when the number average particle size is 0.30 μm or smaller, it becomes difficult to separate the external additive particles from the toner particle surface. The number average particle size of the primary particles of the toner external additive is more preferably 0.05 μm to 0.25 μm, and even more preferably 0.08 μm to 0.18 μm.

[0067] The Young's modulus of the toner external additive is preferably 2000 MPa to 9000 MPa. 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 can be relaxed and external additive particles can be further suppressed from being embedded in the surface of the toner particles.

[0068] When the Young's modulus is 2000 MPa or more, when the toner is subjected to stress from a component such as a carrier, the external additive particles themselves are less likely to be damaged. In addition, when the Young's modulus is 9000 MPa or less, when the toner is subjected to stress from a component such as a carrier, the stress can be easily relieved, and the embedding of the external additive particles into the surface of the toner particles can be further suppressed. Therefore, the surface state of the toner is less likely to change, and changes in the charge of the toner can be further suppressed. The Young's modulus of the external additive for toner is more preferably 3000 MPa to 7000 MPa. The Young's modulus of the external additive for toner can be controlled by changing the mixing ratio of the monomers, the conditions for hydrolysis and condensation, the pH, and the type of catalyst.

[0069] The yield point stress of the external additive for toner is preferably from 1200 MPa to 10000 MPa.

[0070] Under the condition that the yield point stress is 1200 MPa or more, when the toner is subjected to stress from a member such as a carrier, the external additive particles themselves can be suppressed from being destroyed.

[0071] On the other hand, when the yield point stress is 10,000 MPa or less, when the toner is subjected to stress from a member such as a carrier, the stress is easily relieved, and external additive particles can be prevented from being embedded in the surface of the toner particles. Consequently, the surface state of the toner is less likely to change, and changes in the toner charge are easily suppressed.

[0072] The yield point stress is more preferably 1400 MPa to 1800 MPa.The yield point stress of the external additive for toner can be controlled by changing the mixing ratio of monomers, conditions of hydrolysis and condensation, pH, and the type of catalyst.

[0073] The surface of the toner external additive is preferably treated with a hydrophobic agent. Specifically, the particles of the toner external additive are preferably silicone polymer particles surface-treated with a hydrophobic agent. The hydrophobic agent is not particularly limited, but is preferably an organosilicon compound.

[0074] The hydrophobic agent can be exemplified by 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, silicone compounds such as octamethylcyclotetrasiloxane, silicone oil, and silicone varnish.

[0075] By making the surface of the external additive particles hydrophobic, changes in the toner charge level under high-temperature, high-humidity environments can be further suppressed. The toner external additive is preferably surface-treated with at least one compound selected from the group consisting of alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, siloxane compounds, and silicone oil. Furthermore, from the perspective of charge stability, it is more preferred that the toner external additive be surface-treated with an alkylsilazane compound.

[0076] From the viewpoint of charging stability, the hydrophobicity of the external additive for toner obtained by methanol titration is preferably 40% to 80%, more preferably 50% to 60%, and further preferably 50% to 55%.

[0077] In the process of using external additives in toner 29 In the graph obtained by Si-NMR measurement, when the total peak area attributable to the silicon polymer is represented by SA, the peak area attributable to the Q unit structure is represented by S4, the peak area attributable to the T unit structure is represented by S3, and the peak area attributable to the D unit structure is represented by S2, it is preferred that SA, S4, S3 and S2 satisfy the following formulas (I) to (III).

[0078] 0.20≤S4 / SA≤0.60 ...(I)

[0079] 0.00≤S3 / SA≤0.50 ...(II)

[0080] 0.20≤S2 / SA≤0.70 ...(III)

[0081] In the case where formulae (I) to (III) are satisfied, external additive particles can be prevented from being embedded in toner particle surfaces when the toner is subjected to stress from a member such as a carrier, and destruction of the external additive particles themselves can be suppressed.

[0082] Furthermore, more preferably, 0.30 ≤ S4 / SA ≤ 0.50, 0.00 ≤ S3 / SA ≤ 0.10, and 0.50 ≤ S2 / SA ≤ 0.70. Within these ranges, the ratio of Si-OC bonds to siloxane bonds (Si-O-Si) within the external additive particles is optimal, which is more preferred from the perspectives of toner durability stability and charge stability. S4 / SA, S3 / SA, and S2 / SA can be controlled by the selection of the silicon compound, the mixing ratio of the silicon compounds, and the hydrolysis and condensation conditions.

[0083] In the FT-IR spectrum of the external additive for toner obtained by the ATR method, a methylsilyl group is shown at 1200 cm -1 Up to 1300cm -1 The peak at 1250cm-1 is more preferable. -1 Up to 1300cm -1 has a peak in the range of 1250 cm -1 to 1265cm -1 There is a peak in the range of 1250cm -1 Up to 1300cm -1 When a peak is shown within the range, it means that the bonding energy of the methylsilyl group, that is, the mechanical strength is high, and the durable stability and charging stability of the toner are improved.

[0084] From the viewpoint of durable stability and charging stability of the toner, the average circularity of the external additive for toner is preferably 0.850 to 0.950, and more preferably 0.880 to 0.930. The average circularity can be controlled by the mixing ratio of the monomers and the condensation conditions.

[0085] The toner includes toner particles, the toner particles include a binder resin and an external additive for toner, and the external additive for toner is the above-mentioned external additive for toner. From the perspective of charge stability, the content of the external additive for toner in the toner is preferably 0.1 to 20.0 parts by mass per 100 parts by mass of the toner particles. A range of 0.5 to 15.0 parts by mass is more preferred, and a range of 1.0 to 10.0 parts by mass is even more preferred.

[0086] When the content of the toner external additive is 0.1 parts by mass or more, stress applied to the toner can be suppressed, and durable stability and charging stability are improved, even when a large number of low-density images are output for a long period of time under harsh environments such as high temperature and high humidity. Furthermore, when the content of the toner external additive is 20.0 parts by mass or less, filming of the external additive particles on the carrier or photosensitive member can be suppressed, even when high-density images are output for a long period of time.

[0087] <Binder Resin>

[0088] The binder resin used in the toner is not particularly limited, and the following polymers can be used. For example, single polymers of styrene and substituted styrene such as polystyrene, polyparachlorostyrene, and polyvinyltoluene can be used; styrene copolymers such as styrene-parachlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylate copolymers, styrene-methacrylate 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 can be used; and polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral resins, terpene resins, coumarin-indene resins, and petroleum resins can be used. From the perspective of durable stability and charge stability, polyester resins are preferred among the above.

[0089] <Colorant>

[0090] Colorants can be used in toner particles. Colorants can also be contained in toner particles. The following are examples of colorants. Examples of black colorants include carbon black and black colorants obtained by color adjustment by blending a yellow colorant, a magenta colorant, and a cyan colorant. Pigments can be used alone as colorants, but from the perspective of image quality of full-color images, it is preferred to use dyes and pigments together to improve color clarity.

[0091] Examples of magenta pigments 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 and 282; CI Pigment Violet 19; CI Vat Red 1, 2, 10, 13, 15, 23, 29 and 35.

[0092] Examples of magenta dyes include 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; oil-soluble dyes such as 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.

[0093] Examples of cyan pigments include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; CI Acid Blue 45, and copper phthalocyanine pigments having 1 to 5 phthalimide methyl groups substituted on the phthalocyanine skeleton. Examples of cyan dyes include CI Solvent Blue 70.

[0094] Examples of yellow 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, and 185; and CI Vat Yellow 1, 3, and 20. Examples of yellow dyes include CI Solvent Yellow 162. The content of the colorant is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the binder resin.

[0095] <Wax>

[0096] Waxes can be used in toner particles. Examples of waxes include the following: hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline waxes, paraffin waxes, and Fischer-Tropsch waxes; hydrocarbon wax oxides such as oxidized polyethylene waxes, and block copolymers thereof; waxes primarily composed of fatty acid esters such as carnauba wax; and partially or fully deoxygenated fatty acid esters such as deoxygenated carnauba wax.

[0097] Other examples include the following: saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassinoic acid, eleostearic acid, and stearidonic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauba alcohol, wax alcohol, and myrisol; polyols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauba alcohol, wax alcohol, and myrisol; fatty acid amides such as linoleamide, oleamide, and lauramide; and fatty acid amides such as methylene bisstearamide, ethylene biscapric acid amide, ethylene bislauramide, and hexamethylene bisstearamide. Saturated fatty acid bisamides; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'-dioleyladipamide, and N,N'-dioleylsebacamide; aromatic bisamides such as m-xylenebisstearamide and N,N'-distearylisophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; aliphatic hydrocarbon waxes grafted with vinyl monomers such as styrene or acrylic acid; partial esterification products of fatty acids and polyols such as monoglyceride of behenic acid; and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and fats. The wax content is preferably 2.0 to 30.0 parts by mass per 100 parts by mass of the binder resin.

[0098] <Charge Control Agent>

[0099] The toner particles may include a charge control agent as needed. Known charge control agents can be used, but metal compounds of aromatic carboxylic acids are particularly desirable because they are colorless and give toner particles having a fast charging speed and can stably maintain a fixed charge amount.

[0100] Examples of negatively charged charge control agents include salicylic acid metal compounds, benzoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, polymer compounds having sulfonates or sulfonic esters in the side chain, polymer compounds having carboxylates or carboxylates in the side chain, as well as boron compounds, urea compounds, silicon compounds and calixarene.

[0101] Examples of positive charge control agents include quaternary ammonium salts, polymer compounds having quaternary ammonium salts in their side chains, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The amount of the charge control agent added is preferably 0.2 to 10 parts by mass relative to 100 parts by mass of the binder resin.

[0102] <Inorganic fine particles>

[0103] As needed, the toner may also include other inorganic fine particles in addition to the above-mentioned toner external additives. The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner particles as an external additive. When included as an external additive, inorganic fine particles such as fine silica particles, fine titanium oxide particles, and fine aluminum oxide particles are preferred. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0104] As an external additive for improving fluidity, the specific surface area is 50m 2 / g and above and 400m 2 Inorganic fine particles having a specific surface area of ​​1000 Å or less are preferred. Inorganic fine particles having a specific surface area within the above range may be used in combination with an external additive for toner in order to achieve both improvement in fluidity and stabilization of durability.

[0105] The inorganic fine particles are preferably used in an amount of 0.1 to 10.0 parts by mass per 100 parts by mass of the toner particles. When this range is met, the effect of charge stability can be easily achieved. The content of the aforementioned external additive for toner is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, based on the total amount of the external additive.

[0106] <Developer>

[0107] The toner can be used as a single-component developer, but it can also be mixed with a magnetic carrier and used as a two-component developer to further improve dot reproducibility and provide stable images for a long time. That is, in a two-component developer containing a toner and a magnetic carrier, the toner is preferably the above-mentioned toner.

[0108] Magnetic carriers can be made from commonly known materials such as iron oxide, unoxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth metals; alloy particles thereof; and oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) comprising a magnetic material and a binder resin for maintaining the magnetic material in a dispersed state. The mixing ratio of the magnetic carrier to the toner is preferably such that the toner concentration in the two-component developer is 2% to 15% by mass, and more preferably 4% to 13% by mass.

[0109] Method for producing toner particles

[0110] The method for producing the toner particles is not particularly limited, and known production methods such as suspension polymerization, emulsion aggregation, melt kneading, or dissolution suspension methods can be employed. A toner can then be obtained by mixing the toner particles with the aforementioned external additives and, if necessary, other external additives.

[0111] Mixing of the toner particles and the external additive can be accomplished using a mixing device such as a double cone mixer, V-type mixer, drum mixer, super mixer, Henschel mixer, Nauta mixer, Mechano Hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), or Nobilta (manufactured by Hosokawa Micron Corporation).

[0112] From the viewpoint of toner durability stability and charging stability, the Young's modulus of the toner particles is preferably 2000 MPa to 9000 MPa, and more preferably 2800 MPa to 5500 MPa. From the viewpoint of toner durability stability and charging stability, the yield point stress of the toner particles is preferably 500 MPa to 10000 MPa, and more preferably 600 MPa to 1600 MPa.

[0113] The measurement methods of various physical properties will be described below.

[0114] <Separation of External Additive Particles and Toner Particles from Toner>

[0115] Each physical property can also be measured by using an external additive separated from the toner using the following method. A total of 200g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100mL of ion exchange water and dissolved in a hot water bath to prepare a sucrose concentrate. 31g of sucrose concentrate and 6mL of Contaminone N (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments; pH 7 and including 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. A total of 1g of toner is added to the dispersion, and the toner lumps are loosened with a scraper or the like.

[0116] The centrifuge tube was shaken for 20 minutes at 350 vibrations per minute using a shaker ("KM Shaker" (model: V.SX), manufactured by Iwaki Sangyo Co., Ltd.). After shaking, the solution was transferred to a glass tube (50 mL) for a swing rotor and centrifuged at 3500 rpm for 30 minutes using a centrifuge.

[0117] In the glass tube after centrifugation, the toner is present in the topmost layer, and the toner external additive is present in the aqueous solution side of the lower layer. The aqueous solution in the lower layer is collected and centrifuged to separate the sucrose and the toner external additive, and the toner external additive is collected. Centrifugation is repeated as needed, and after sufficient separation, the dispersion is dried and the toner external additive is collected. When adding multiple toner external additives, the toner external additive can be selected using centrifugation or other methods.

[0118] <Method for measuring the number average particle size of primary particles of external additives for toner>

[0119] The number average particle size of the primary particles of the external additive for toner is measured according to the centrifugal sedimentation method. Specifically, 0.01 g of dried external additive particles are placed in a 25 ml glass vial, and 0.2 g of a 5% Triton solution and 19.8 g of RO water are added thereto to produce a solution. Next, the probe (the tip in the front terminal) of the ultrasonic disperser is immersed in the solution to induce ultrasonic dispersion for 15 minutes at an output of 20 W, and a dispersion is obtained as a result. The dispersion is then used to measure the number average particle size of the primary particles with the help of a centrifugal sedimentation force distribution measuring device DC24000 from CPS Instruments Inc. The disk rotation speed is set to 18000 rpm, and the true density is set to 1.3 g / cm 3Before the measurement, the device was calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0120] Method for measuring the softening temperature (Tm) of binder resin

[0121] The softening temperature of the resin is measured using a constant-load extrusion capillary rheometer, the "Flow Tester CFT-500D" (flow characteristics evaluation device, manufactured by Shimadzu Corporation), according to the manual that comes with the device. In this device, the temperature of a measurement sample filled in a cylinder is raised and the sample is melted while a constant load is applied from the top of the measurement sample by a piston. The molten measurement sample is then extruded from a die at the bottom of the cylinder. A flow curve showing the relationship between the piston's descending amount and the temperature is obtained.

[0122] In the present disclosure, the "melting temperature in the 1 / 2 method" described in the manual attached to the "Flow Tester CFT-500D" (flow characteristics evaluation device) is defined as the softening temperature (Tm). The melting temperature in the 1 / 2 method is calculated as follows.

[0123] First, 1 / 2 of the difference between the piston drop at the end of outflow (outflow end, Smax) and the piston drop at the start of outflow (lowest point, Smin) is calculated (represented by X; X = (Smax - Smin) / 2). The temperature of the flow curve when the piston drop is the sum of X and Smin is defined as the melting temperature according to the 1 / 2 method.

[0124] A cylindrical measurement sample having a diameter of 8 mm was prepared by compression molding approximately 1.0 g of resin at 10 MPa for 60 seconds at 25° C. using a tablet molding press (e.g., a standard manual Newton Press NT-100H, manufactured by NPA System Co., Ltd.). Specific measurement procedures were performed according to the manual included with the device.

[0125] The measurement conditions of CFT-500D are as follows.

[0126] Test mode: heating method

[0127] Starting temperature: 50℃

[0128] Reaching temperature: 200℃

[0129] Measuring interval: 1.0℃

[0130] Heating rate: 4.0℃ / min

[0131] Piston cross-sectional area: 1.000cm 2

[0132] Test load (piston load): 10.0 kgf (0.9807 MPa)

[0133] Warm-up time: 300 seconds

[0134] Mold aperture: 1.0mm

[0135] Mold length: 1.0mm

[0136] Method for measuring weight average particle size (D4) of toner particles

[0137] The weight-average particle diameter (D4) of the toner particles is determined by performing measurement in 25,000 channels with an effective number of measurement channels and performing analysis of the measurement data, using a "Coulter Counter Multisizer 3" (registered trademark, Beckman Coulter, Inc.) which is a precision particle size distribution measuring instrument operating based on the pore resistance method and equipped with a 100 μm aperture tube, and using attached dedicated software, i.e., "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter, Inc.), to set measurement conditions and analyze the measurement data.

[0138] The electrolyte aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to provide a concentration of approximately 1 mass %, and for example, "ISOTON II" (Beckman Coulter, Inc.) can be used. Dedicated software is set as follows before measurement and analysis.

[0139] In the "Change Standard Operating Method (SOM)" screen of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to that obtained using "Standard Particles 10.0 μm" (Beckman Coulter, Inc.). The threshold and noise level were automatically set by pressing the Threshold / Noise Level Measurement button. Additionally, set the current to 1,600 μA, the gain to 2, the electrolyte solution to ISOTON II, and check the "Post-measurement Orifice Flushing" checkbox.

[0140] In the "Set Pulse to Size Conversion" screen of the dedicated software, set the element spacing to logarithmic size, the size element to 256 size elements, and the size range to 2 μm to 60 μm. The specific measurement steps are as follows.

[0141] (1) Approximately 200 ml of the above electrolyte aqueous solution was introduced into a 250 mL round-bottom glass beaker dedicated to the Multisizer 3, placed on the sample stage, and stirred counterclockwise at 24 revolutions per second using a stirring rod. Dirt and bubbles were initially removed from the nozzle using the "Nozzle Rinse" function of the dedicated software.

[0142] (2) About 30 ml of the electrolyte aqueous solution was introduced into a 100 mL flat-bottom glass beaker. About 0.3 mL of a dilution solution prepared by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral pH 7 detergent for cleaning precision measuring instruments comprising a nonionic surfactant, an anionic surfactant, and an organic builder, available from Wako Pure Chemical Industries, Ltd.) with three times the mass of deionized water was added thereto as a dispersant.

[0143] (3) A predetermined amount of deionized water was introduced into a water tank of an ultrasonic disperser "Ultrasonic DispersionSystem Tetora 150" (Nikkaki Bios Co., Ltd.) having a power output of 120 W and equipped with two oscillators (oscillation frequency = 50 kHz) configured so as to be 180° phase-shifted, and approximately 2 mL of Contaminon N was added to the water tank.

[0144] (4) The beaker described in (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is started. The vertical position of the beaker is adjusted in such a way that the liquid surface resonance state of the electrolyte aqueous solution in the beaker is maximized.

[0145] (5) While ultrasonic waves are being irradiated on the electrolyte aqueous solution in the beaker set up according to (4), approximately 10 mg of toner particles are added in small amounts to the electrolyte aqueous solution and dispersed. The ultrasonic dispersion treatment is continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately controlled to 10°C to 40°C.

[0146] (6) Using a pipette, the aqueous electrolyte solution containing dispersed toner particles prepared in (5) is added dropwise to the round-bottom flask set in the sample stage as described in (1), adjusted to provide a measurement concentration of approximately 5%. Measurement is then performed until the number of particles measured reaches 50,000.

[0147] (7) Analyze the measurement data using the dedicated software included with the device and calculate the weight-average particle size (D4). 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).

[0148] <Method for Measuring Average Circularity of Toner External Additive Particles, Toner Particles, and Toner>

[0149] The average circularity is a simple method for quantitatively expressing particle shape. Particles with an equivalent circular diameter ranging from 0.01 μm to 400 μm are measured using a flow-type particle image analyzer, FPIA-3000, manufactured by Sysmex Corporation. The circularity of the measured particles is determined by the following formula, and the value obtained by dividing the total circularity by the total number of particles is defined as the average circularity. The number of particles to be measured is 5,000.

[0150] Circularity a=L0 / L

[0151] (where L0 represents the circumference of a circle having the same projected area as the particle image, and L represents the circumference of the particle projection image when image processing is performed at an image processing resolution of 512×512 (pixels of 0.3 μm×0.3 μm)).

[0152] Method for measuring FT-IR spectrum of external additives for toners

[0153] The FT-IR spectrum was measured by the ATR method using a Fourier transform infrared spectrometer (Spectrum One: manufactured by PerkinElmer Co.) equipped with a universal ATR sampling accessory. The specific measurement steps are as follows. The incident angle of infrared light (λ = 5 μm) was set to 45°. As the ATR crystal, a Ge ATR crystal (refractive index = 4.0) was used. Other conditions are as follows.

[0154] scope

[0155] Start: 4000cm -1

[0156] End: 600cm -1

[0157] Duration

[0158] Number of scans: 16

[0159] Resolution: 4.00cm -1

[0160] Pre-calibration: with CO2 / H2O

[0161] (1) A Ge ATR crystal (refractive index = 4.0) was mounted on the device.

[0162] (2) Set the scan type to background, set the unit to EGY, and measure the background.

[0163] (3) Set the Scan Type to Sample and the Unit to A.

[0164] (4) A total of 0.01 g of sample was weighed onto the ATR crystal.

[0165] (5) Use the pressure arm to pressurize the sample (dynamometer to 90).

[0166] (6) Measure the sample.

[0167] (7) The obtained FT-IR spectra were baseline corrected by automatic calibration.

[0168] (8) Calculate 600cm -1 Up to 4000cm -1 The maximum value and wave number of the absorption peak intensity within the range are determined, and the position of the maximum peak is confirmed.

[0169] (9) Calculate 1015cm -1 Up to 1025cm -1 The average value of the absorption peak intensity within the range (A).

[0170] (10) Calculate 1085cm -1 to 1095cm -1 The average value of the absorption peak intensity within the range (B).

[0171] A / B is calculated using A and B obtained as described above.

[0172] In addition, in the obtained spectrum, at 1200 cm -1 Up to 1300cm -1 Confirm the presence or absence of absorption peak within the range of 1200cm -1 Up to 1300cm -1 The absorption peak in the range of 1250cm represents the stretching vibration of Si-CH3. Si-CH3 is a hydrophobic functional group, and from the perspective of improving the charging stability in a high humidity environment, it is preferable to have an absorption peak in this range. In addition, from the perspective of durable stability, it is preferable to have an absorption peak at 1250cm -1 Up to 1300cm -1 There is a peak in the range of .

[0173] <Method for measuring hydrophobicity of external additives for toner>

[0174] The hydrophobicity of the toner external additive was calculated using methanol titration. Specifically, the hydrophobicity was measured using the following procedure. Methanol was added dropwise from a burette to a mixture obtained by adding 0.5 g of toner external additive particles to 50 ml of RO until the entire amount of the toner external additive was wetted. The addition was performed while the mixture was stirred.

[0175] Whether the entire amount is wetted is determined by whether the entire amount of the toner external additive suspended on the water surface is immersed in the liquid and suspended in the liquid. The volume percentage of methanol in the total amount of methanol added and the mixed liquid at the end of the dropwise addition is taken as the hydrophobicity. A higher hydrophobicity indicates a higher hydrophobicity.

[0176] <Through solid state 29 Si-NMR method for measuring the abundance ratio of constituent compounds of external additives for toners>

[0177] In solid state 29 In Si-NMR, peaks are detected in shift regions that vary depending on the structure of the functional groups bonded to Si in the compounds that constitute the toner external additive. By using standard samples to identify the position of each peak, the Si-bonded structure can be specified. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak areas. The ratio of the peak areas for the Q unit structure, T unit structure, and D unit structure to the total peak area can be calculated.

[0178] Specifically, solid-state 29 The measurement conditions of Si-NMR are as follows.

[0179] Instrument: JNM-ECX5002 (JEOL RESONANCE)

[0180] Temperature: Room temperature

[0181] Measurement method: DDMAS method 29 Si 45°

[0182] Sample tube: Zirconia, diameter 3.2mm

[0183] Sample: Filled in sample tube in powder form

[0184] Sample speed: 10kHz

[0185] Relaxation delay: 180s

[0186] Scans: 2000

[0187] After measurement, peaks of the M unit structure, D unit structure, T unit structure, and Q unit structure are separated by curve fitting of a plurality of silane components having different substituents and bonding groups of the sample or external additive for toner, and the area of ​​each peak is calculated.

[0188] Curve fitting was performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series) software for the JNM-EX400 manufactured by JEOL Ltd. The measurement data was read by clicking "1D Pro" from the menu icon. Next, "Curve Fitting Function" was selected from "Command" on the menu bar, and curve fitting was performed. Curve fitting of each component was performed so that the difference between the combined peaks (combined peak difference) obtained by combining the peaks obtained by curve fitting and the peaks of the measurement results was minimized.

[0189] M unit structure: (Ra)(Rb)(Rc)SiO 1 / 2 (S1)

[0190] D unit structure: (Rd)(Re)Si(O 1 / 2 )2 (S2)

[0191] T unit structure: RfSi(O 1 / 2 )3 (S3)

[0192] Q unit structure: Si(O 1 / 2 )4 (S4)

[0193] (S1+S2+S3+S4)=SA.

[0194] In formulas (S1), (S2) and (S3), Ra, Rb, Rc, Rd, Re and Rf are each an organic group such as a hydrocarbon group (e.g., an alkyl group) having 1 to 6 carbon atoms or a halogen atom bonded to silicon. When the structure must be confirmed in more detail, 13 C-NMR and 1 The results of H-NMR measurements are consistent with 29 The Si-NMR measurement results were identified together. S2 / SA, S3 / SA, and S4 / SA were calculated from the thus obtained SA, S2, S3, and S4.

[0195] Method for confirming surface treatment agent used as external additive for toner

[0196] The surface treatment agent used for the external additive for toner is analyzed by pyrolysis-GC-MS (gas chromatography-mass spectrometry). Specifically, the measurement conditions are as follows.

[0197] Instrument: GC6890A (manufactured by Agilent Technologies, Inc.), pyrolyzer (manufactured by Japan Analytical Industry Co., Ltd.)

[0198] Column: HP-5ms 30m

[0199] Pyrolysis temperature: 590℃

[0200] By specifying each peak position of the profile obtained by measurement using a standard sample, the surface treatment agent for the external additive for toner is specified.

[0201] Method for measuring Young's modulus and yield point stress of external additive for toner and toner particles

[0202] The Young's modulus and yield point stress of the external additive for toner and the toner particles can be obtained from a micro compression test using Hysitron PI 85L PicoIndenter (manufactured by Bruker Co.).

[0203] Young's modulus (MPa) is calculated from the slope of the displacement (nm) and the test force (μN) profile (load-displacement curve) obtained by measurement. Furthermore, the yield point stress (MPa) is calculated from the yield point (change point) of the profile. Specifically, the yield point stress is calculated by dividing the stress applied to the measuring indenter at the yield point by the area of ​​the measuring surface of the measuring indenter.

[0204] - Fixtures / Fixtures

[0205] Base system: Hysitron PI 85L

[0206] Measuring indenter: Flat-end indenter with a rounded tip of 1 μm in diameter

[0207] SEM used: Thermo Fisher Versa 3D

[0208] SEM conditions: -10° tilt, 13pA at 10keV

[0209] -Measurement conditions

[0210] Measuring mode: displacement control

[0211] Maximum displacement: 30nm

[0212] Displacement speed: 1nm / s

[0213] Hold time: 2 seconds

[0214] Unloading speed: 5nm / s

[0215] -Analysis methods

[0216] Hertz analysis was applied to the load-displacement curve obtained when compressed from 0 nm to 10 nm, and the Young's modulus and yield point stress of each particle were calculated.

[0217] -Sample conditioning

[0218] Use silicon wafers with external toner additives or attached toner particles.

[0219] Example

[0220] The present invention will be described in more detail with reference to the examples shown below. However, these examples are not intended to limit the present invention in any way. Unless otherwise indicated, the expression "parts" in the following formulations are by mass in all cases.

[0221] <Production Example of Toner External Additive Particles 1>

[0222] 1. Hydrolysis step

[0223] A total of 43.2 g of RO water and 0.008 g of acetic acid as a catalyst were put into a 200 ml beaker and stirred at 45° C. 27.2 g of tetraethoxysilane and 27.2 g of dimethyldimethoxysilane were added thereto, followed by stirring for 1.5 hours to obtain a raw material solution.

[0224] 2. Polycondensation step

[0225] A total of 68.8 g of RO water, 340.0 g of methanol, and 2.0 g of 25% aqueous ammonia were placed in a 1000 ml beaker and stirred at 30°C to prepare an alkaline aqueous medium. The raw material solution obtained in "1. Hydrolysis Step" was added dropwise to the alkaline aqueous medium over 1 minute. The resulting mixture was stirred at 30°C for 1.5 hours to promote the polycondensation reaction and obtain a polycondensation reaction solution.

[0226] 3. Particle Formation Step

[0227] A total of 1000 g of RO water was placed in a 2000 ml beaker and stirred at 25°C. The polycondensation reaction solution obtained in "2. Polycondensation Step" was added dropwise over 10 minutes. The polycondensation reaction solution became turbid upon mixing with water, and a dispersion containing silicon polymer particles having siloxane bonds was obtained.

[0228] 4. Hydrophobization step

[0229] A total of 27.1 g of hexamethyldisilazane as a hydrophobic agent was added to the dispersion liquid including silicon polymer particles having siloxane bonds obtained in "3. Particle formation step", followed by stirring at 60°C for 2.5 hours. After the dispersion liquid was allowed to stand for 5 minutes, the powder precipitated at the bottom of the solution was collected by suction filtration and dried at 120°C under reduced pressure for 24 hours to obtain external additive particles 1 for toner. The number average particle size of the primary particles of the obtained external additive particles 1 for toner was 0.12 μm. Table 1 shows the physical properties of the external additive particles 1 for toner. The FT-IR spectrum of the external additive particles 1 for toner shows Figure 1 middle.

[0230] <Production Example of Toner External Additive Particles 2>

[0231] Toner External Additive Particles 2 were obtained in the same manner as in Production Example of Toner External Additive Particles 1 except that the amount of hexamethyldisilazane used in the hydrophobization step was changed to 16.3 g. Table 1 shows the physical properties of the obtained Toner External Additive Particles 2.

[0232] <Production Example of Toner External Additive Particles 3>

[0233] Toner External Additive Particles 3 were obtained in the same manner as in Production Example of Toner External Additive Particles 1 except that the amount of hexamethyldisilazane used in the hydrophobization step was changed to 37.9 g. Table 1 shows the physical properties of the obtained Toner External Additive Particles 3.

[0234] <Production Example of Toner External Additive Particles 4>

[0235] Toner External Additive Particles 4 were obtained in the same manner as in the Production Example of Toner External Additive Particles 1, except that the stirring temperature in the hydrolysis step was changed to 50° C. and the amount of 25% ammonia water used in the polycondensation step was changed to 1.5 g. Table 1 shows the physical properties of the obtained Toner External Additive Particles 4.

[0236] <Production Example of Toner External Additive Particles 5>

[0237] Toner External Additive Particles 5 were obtained in the same manner as in the Production Example of Toner External Additive Particles 1, except that the stirring temperature in the hydrolysis step was changed to 40° C. and the amount of 25% ammonia water used in the polycondensation step was changed to 2.3 g. Table 1 shows the physical properties of the obtained Toner External Additive Particles 5.

[0238] <Production Example of Toner External Additive Particles 6>

[0239] Toner External Additive Particles 6 were obtained in the same manner as in the Production Example of Toner External Additive Particles 1, except that the stirring temperature in the hydrolysis step was changed to 50° C., and in the polycondensation step, the amount of RO water was changed to 98.8 g, the amount of methanol was changed to 310.0 g, and the amount of 25% ammonia water was changed to 1.5 g. Table 1 shows the physical properties of the obtained Toner External Additive Particles 6.

[0240] <Production Example of Toner External Additive Particles 7>

[0241] Toner External Additive Particles 7 were obtained in the same manner as in the Production Example of Toner External Additive Particles 1, except that the stirring temperature in the hydrolysis step was changed to 40° C., and in the polycondensation step, the amount of RO water was changed to 58.8 g, the amount of methanol was changed to 350.0 g, and the amount of 25% ammonia water was changed to 2.5 g. Table 1 shows the physical properties of the obtained Toner External Additive Particles 7.

[0242] <Production Example of Toner External Additive Particles 8>

[0243] Table 1 shows the physical properties of the obtained Toner External Additive Particles 8.

[0244] <Production Example of Toner External Additive Particles 9>

[0245] Table 1 shows the physical properties of the obtained Toner External Additive Particles 9.

[0246] <Production Example of Toner External Additive Particles 10>

[0247] Toner external additive particles 10 were obtained in the same manner as in the production example of toner external additive particles 1, except that the stirring time in the hydrolysis step was changed to 1.0 hour, and the stirring time of the mixed solution after the dropwise addition of the raw material solution in the polycondensation step was changed to 1.0 hour. Table 1 shows the physical properties of the obtained toner external additive particles 10.

[0248] <Production Example of Toner External Additive Particles 11>

[0249] Toner External Additive Particles 11 were obtained in the same manner as in the Production Example of Toner External Additive Particles 1, except that the stirring time in the hydrolysis step was changed to 2.0 hours, and the stirring time of the mixed solution after the dropwise addition of the raw material solution in the polycondensation step was changed to 2.0 hours. Table 1 shows the physical properties of the obtained Toner External Additive Particles 11.

[0250] <Production Example of Toner External Additive Particles 12>

[0251] Toner External Additive Particles 12 were obtained in the same manner as in Production Example of Toner External Additive Particles 1, except that the hydrophobizing agent used in the hydrophobizing step was changed to octamethylcyclotetrasiloxane. Table 1 shows the physical properties of the obtained Toner External Additive Particles 12.

[0252] <Production Example of Toner External Additive Particles 13>

[0253] Toner External Additive Particles 13 were obtained in the same manner as in Production Example of Toner External Additive Particles 1, except that the hydrophobizing agent used in the hydrophobizing step was changed to chlorotrimethylsilane. Table 1 shows the physical properties of the obtained Toner External Additive Particles 13.

[0254] <Production Example of Toner External Additive Particles 14>

[0255] Toner External Additive Particles 14 were obtained in the same manner as in Production Example of Toner External Additive Particles 1, except that the hydrophobizing agent used in the hydrophobizing step was changed to trifluoropropyltrimethoxysilane. Table 1 shows the physical properties of the obtained Toner External Additive Particles 14.

[0256] <Production Example of Toner External Additive Particles 15>

[0257] Toner External Additive Particles 15 were obtained in the same manner as in Production Example of Toner External Additive Particles 1, except that the hydrophobizing agent used in the hydrophobizing step was changed to dimethyl silicone oil. Table 1 shows the physical properties of the obtained Toner External Additive Particles 15.

[0258] <Production Example of Toner External Additive Particles 16>

[0259] Toner External Additive Particles 16 were obtained in the same manner as in the Production Example of Toner External Additive Particles 1, except that no hydrophobizing agent was added in the hydrophobizing step. Table 1 shows the physical properties of the obtained Toner External Additive Particles 16.

[0260] <Production Example of Toner External Additive Particles 17>

[0261] In the hydrolysis step, the amount of tetraethoxysilane was changed to 30.1 g and the amount of dimethyldimethoxysilane was changed to 24.3 g. In the same manner as in the production example of the toner external additive particles 1, toner external additive particles 17 were obtained. Table 1 shows the physical properties of the obtained toner external additive particles 17.

[0262] <Production Example of Toner External Additive Particles 18>

[0263] In the hydrolysis step, the amount of tetraethoxysilane was changed to 23.5 g and the amount of dimethyldimethoxysilane was changed to 30.9 g, and the toner external additive particles 18 were obtained in the same manner as in the production example of the toner external additive particles 1. Table 1 shows the physical properties of the obtained toner external additive particles 18.

[0264] <Production Example of Toner External Additive Particles 19>

[0265] In the hydrolysis step, the amount of tetraethoxysilane was changed to 33.8 g and the amount of dimethyldimethoxysilane was changed to 20.6 g, and the toner external additive particles 19 were obtained in the same manner as in the production example of the toner external additive particles 1. Table 1 shows the physical properties of the obtained toner external additive particles 19.

[0266] <Production Example of Toner External Additive Particles 20>

[0267] Toner external additive particles 20 were obtained in the same manner as in the production example of toner external additive particles 1, except that the stirring time in the hydrolysis step was changed to 2.0 hours, and the stirring time of the mixed solution after the dropwise addition of the raw material solution in the polycondensation step was changed to 2.5 hours. Table 1 shows the physical properties of the obtained toner external additive particles 20.

[0268] <Production Example of Toner External Additive Particles 21>

[0269] Toner External Additive Particles 21 were obtained in the same manner as in the Production Example of Toner External Additive Particles 1, except that the stirring temperature and stirring time in the hydrolysis step were changed to 35° C. and 1.0 hour, respectively, and the stirring time of the mixed solution after the dropwise addition of the raw material solution in the polycondensation step was changed to 1.0 hour. Table 1 shows the physical properties of the obtained Toner External Additive Particles 21.

[0270] <Production Example of Toner External Additive Particles 22>

[0271] Toner external additive particles 22 were obtained in the same manner as in the production example of toner external additive particles 1, except that in the hydrolysis step, the amount of tetraethoxysilane was changed to 16.9 g, the amount of dimethyldimethoxysilane was changed to 18.6 g, 18.9 g of trimethoxymethylsilane was further added, the stirring temperature was changed to 30° C., and the stirring time was changed to 0.5 h. Table 1 shows the physical properties of the obtained toner external additive particles 22.

[0272] <Production Example of Toner External Additive Particles 23>

[0273] Toner external additive particles 23 were obtained in the same manner as in the production example of toner external additive particles 1, except that in the hydrolysis step, the amount of tetraethoxysilane was changed to 30.1 g, the amount of dimethyldimethoxysilane was changed to 8.2 g, 16.1 g of trimethoxymethylsilane was further added, the stirring temperature was changed to 30° C., and the stirring time was changed to 0.5 h. Table 1 shows the physical properties of the obtained toner external additive particles 23.

[0274] <Production Example of Toner External Additive Particles 24>

[0275] Toner external additive particles 24 were obtained in the same manner as in the production example of toner external additive particles 1, except that in the hydrolysis step, the amount of tetraethoxysilane was changed to 15.4 g, the amount of dimethyldimethoxysilane was changed to 8.2 g, 30.8 g of trimethoxymethylsilane was further added, the stirring temperature was changed to 30° C., and the stirring time was changed to 0.5 h. Table 1 shows the physical properties of the obtained toner external additive particles 24.

[0276] <Production Example of Toner External Additive Particles 25>

[0277] In the hydrolysis step, the amount of tetraethoxysilane was changed to 22.1 g, the amount of dimethyldimethoxysilane was changed to 21.6 g, and 10.7 g of trimethylsilanol was further added. Toner external additive particles 25 were obtained in the same manner as in the production example of toner external additive particles 1. Table 1 shows the physical properties of the obtained toner external additive particles 25.

[0278] <Production Example of Toner External Additive Particles 26>

[0279] In the hydrolysis step, 54.4 g of trimethoxymethylsilane was added instead of tetraethoxysilane and dimethyldimethoxysilane, the stirring temperature was changed to 30° C., and the stirring time was changed to 0.5 h. Toner external additive particles 26 were obtained in the same manner as in the production example of toner external additive particles 1. Table 1 shows the physical properties of the obtained toner external additive particles 26. The FT-IR spectrum of the toner external additive particles 26 shows Figure 2 middle.

[0280] <Production Example of Toner External Additive Particles 27>

[0281] Toner external additive particles 27 were obtained in the same manner as in the production example of toner external additive particles 26 except that the amount of trimethoxymethylsilane was changed to 50.6 g and 3.8 g of tetraethoxysilane was added. Table 1 shows the physical properties of the obtained toner external additive particles 27.

[0282] <Production Example of Toner External Additive Particles 28>

[0283] Toner external additive particles 28 were obtained in the same manner as in the production example of toner external additive particles 26 except that the amount of trimethoxymethylsilane was changed to 45.2 g and 9.2 g of dimethyldimethoxysilane was added. Table 1 shows the physical properties of the obtained toner external additive particles 28.

[0284] <Production Example of Toner External Additive Particles 29>

[0285] A total of 124.0 g of ethanol, 24.0 g of RO water, and 10.0 g of 28% aqueous ammonia were added to a 2000 ml beaker, 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 h. After the addition was complete, the mixture was further stirred for 0.5 h and hydrolyzed to obtain a dispersion of silicon polymer particles having siloxane bonds.

[0286] After adding 95.0 g of hexamethyldisilazane to the dispersion of the silicon polymer particles having siloxane bonds obtained in the above step at room temperature, the dispersion was heated from 50° C. to 60° C. and stirred for 3.0 hours. Then, the powder in the dispersion was collected by suction filtration and dried at 120° C. for 24 hours under reduced pressure to obtain toner external additive particles 29. Table 1 shows the physical properties of the obtained toner external additive particles 29. The FT-IR spectrum of the toner external additive particles 29 shows Figure 3 middle.

[0287] <Production Example of Toner External Additive Particles 30>

[0288] Toner external additive particles 30 were obtained in the same manner as in the production example of toner external additive particles 29 except that the amount of tetraethoxysilane was changed to 208.8 g and 23.2 g of trimethoxymethylsilane was added. Table 1 shows the physical properties of the obtained toner external additive particles 30.

[0289] [Table 1]

[0290]

[0291] In the table, the monomer composition shows the molar ratio. DH represents hydrophobicity. MPP represents the maximum peak position, which is the maximum peak (cm -1 ) position. X indicates the position at 1200cm -1 Up to 1300cm -1 The position of the peak within the range is used, and "none" is used when there is no peak. YM represents Young's modulus, YP represents yield point stress, PD represents "number average particle diameter of primary particles", and AC represents average circularity.

[0292] <Production Example of Polyester Resin A1>

[0293] - 76.9 parts (0.167 mol) of polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane

[0294] - 25.0 parts (0.145 mol parts) of terephthalic acid (TPA)

[0295] - 8.0 parts (0.054 mol) of adipic acid

[0296] - 0.5 parts of n-butyl titanate

[0297] The above materials were placed in a 4-liter glass four-necked flask. A thermometer, stirring rod, condenser, and nitrogen inlet tube were attached to the flask, and the flask with accessories was placed in a jacket heater. Next, the interior of the flask was replaced with nitrogen, the temperature was gradually increased while stirring, and the reaction was carried out at 200°C with stirring for 4 hours. Thereafter, 1.2 parts (0.006 mol) of trimellitic anhydride (TMA) was added and the reaction was carried out at 180°C for 1 hour to obtain polyester resin A1. The softening temperature of polyester resin A1 was 90°C.

[0298] <Production Example of Polyester Resin A2>

[0299] - Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts (0.155 mol)

[0300] -24.1 parts (0.145 mol) of terephthalic acid

[0301] - 0.6 parts of n-butyl titanate

[0302] The above materials were placed in a 4-liter glass four-necked flask. A thermometer, stirring rod, condenser, and nitrogen inlet tube were attached to the flask, and the flask with accessories was placed in a jacket heater. Next, the interior of the flask was replaced with nitrogen, the temperature was gradually increased while stirring, and the reaction was carried out at 200°C with stirring for 2 hours. Thereafter, 5.8 parts (0.030 mol) of trimellitic anhydride was added and the reaction was carried out at 180°C for 10 hours to obtain polyester resin A2. The softening temperature of polyester resin A2 was 130°C.

[0303] <Production Example of Toner Particles 1>

[0304] - 70.0 parts of polyester resin A1

[0305] - 30.0 parts of polyester resin A2

[0306] -Fischer-Tropsch wax (peak temperature of maximum endothermic peak is 78°C) 5.0 parts

[0307] -CI Pigment Blue 15:3 5.0 parts

[0308] -0.1 part of 3,5-di-tert-butylsalicylic acid aluminum compound

[0309] A Henschel mixer (FM-75, manufactured by Nippon Coke & Engineering Co., Ltd.) was used for 20 s. -1 The raw materials of the above formulation were mixed at a rotation speed of 1000 rpm and a rotation time of 5 minutes, and then kneaded using a twin-screw kneader (PCM-30 model, manufactured by Ikegai Corp.) set to a temperature of 125° C. and a rotation speed of 300 rpm. The obtained kneaded product was cooled and coarsely pulverized with a hammer mill to a diameter of 1 mm or less to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Corporation).

[0310] Furthermore, a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) was used for classification to obtain toner particles 1. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) referred to herein were as follows: the rotation speed of the classifying rotor was 50.0 s -1 The following is graded.

[0311] The obtained toner particles 1 had a weight average particle diameter (D4) of 5.9 μm, a Young's modulus of 4000 MPa, and a yield point stress of 1000 MPa.

[0312] <Production Example of Toner Particles 2>

[0313] Toner Particles 2 were obtained in the same manner as in the Production Example of Toner Particles 1, except that the amount of the polyester resin A1 was changed to 85.0 parts and the amount of the polyester resin A2 was changed to 15.0 parts. The obtained Toner Particles 2 had a weight-average particle diameter (D4) of 5.9 μm, a Young's modulus of 3000 MPa, and a yield point stress of 700 MPa.

[0314] <Production Example of Toner Particles 3>

[0315] Toner Particles 3 were obtained in the same manner as in the Production Example of Toner Particles 1, except that the amount of the polyester resin A1 was changed to 60.0 parts and the amount of the polyester resin A2 was changed to 40.0 parts. The obtained Toner Particles 3 had a weight-average particle diameter (D4) of 5.9 μm, a Young's modulus of 5000 MPa, and a yield point stress of 1200 MPa.

[0316] <Production Example of Toner Particles 4>

[0317] Preparation of styrene acrylic resin particle dispersion

[0318] A total of 89.5 parts of styrene, 9.2 parts of butyl acrylate, 1.3 parts of acrylic acid, 3.2 parts of n-lauryl mercaptan are mixed and dissolved. An aqueous solution prepared by mixing 1.5 parts of Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) with 150 parts of ion exchange water is added to the mixed solution, and then dispersed. While slowly stirring for 10 minutes, an aqueous solution prepared by mixing 0.3 parts of potassium persulfate with 10 parts of ion exchange water is further added. After nitrogen replacement, emulsion polymerization is carried out at 70 ° C for 6h. After completion of polymerization, the reaction solution is cooled to room temperature, and ion exchange water is added to obtain a styrene acrylic resin particle dispersion.

[0319] Preparation of release agent dispersion

[0320] A total of 100 parts of a release agent (behenyl behenate, melting point: 72.1° C.) and 15 parts of Neogen RK were mixed with 385 parts of ion-exchanged water and dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Tsunemitsu Co., Ltd.) to obtain a release agent dispersion. The solid content concentration of the release agent dispersion was 20% by mass.

[0321] Preparation of colorant dispersion

[0322] A total of 100 parts of CI Pigment Blue 15:3 and 15 parts of Neogen RK were mixed with 885 parts of ion-exchanged water and dispersed using a wet jet mill JN100 for about 1 hour to obtain a colorant dispersion liquid.

[0323] Preparation of Toner Particles 4

[0324] A total of 265 parts of styrene acrylic resin particle dispersions, 10 parts of release agent dispersions, and 10 parts of colorant dispersions were placed in a container and dispersed using a homogenizer (ULTRA-TURRAX T50, manufactured by IKA). The temperature inside the container was adjusted to 30°C under stirring, and 1 mol / L hydrochloric acid was added to adjust the pH to 5.0. After standing for 3 minutes, heating was started and raised to 50°C to generate aggregated particles. In this state, the particle size of the aggregated particles was measured using a "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter Inc.).

[0325] When the weight-average particle size of the aggregated particles reached 6.2 μm, a 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 8.0 to stop particle growth. The temperature was then raised to 95°C, and the aggregated particles were fused and sphericalized. When the average circularity reached 0.980, the temperature was lowered to 30°C to obtain Toner Particle Dispersion Liquid 1.

[0326] Hydrochloric acid was added to the resulting toner particle dispersion 1 to adjust the pH to 1.5 or less, and the mixture was stirred for 1 hour before undergoing solid-liquid separation using a pressure filter to obtain a toner filter cake. This was reslurried with ion-exchanged water to form a dispersion again, and then subjected to solid-liquid separation using the aforementioned filter. Reslurrying and solid-liquid separation were repeated until the filtrate had an electrical conductivity of 5.0 μS / cm or less, and then solid-liquid separation was finally performed to obtain a toner filter cake.

[0327] The obtained toner cake was dried using a Flash Jet Dryer (manufactured by Seishin Enterprise Co., Ltd.). Drying conditions were an air blow temperature of 90°C and a dryer outlet temperature of 40°C. The toner cake feed rate was adjusted to a rate that did not deviate from the outlet temperature of 40°C, depending on the water content of the toner cake. Furthermore, fine powder and coarse powder were separated using a multi-stage classifier utilizing the Coanda effect to obtain Toner Particles 4. The obtained Toner Particles 4 had a weight-average particle size (D4) of 5.9 μm, a Young's modulus of 4500 MPa, and a yield stress of 1400 MPa.

[0328] <Production Example of Toner 1>

[0329] -Toner particles 1 100 parts

[0330] - 6.0 parts of external additive particles for toner

[0331] The mixture was stirred for 30 s using a Henschel mixer model FM-10C (manufactured by Mitsui Miike Machinery Co., Ltd.). -1 The above materials were mixed at a rotation speed of 0.05 and a rotation time of 10 minutes to obtain Toner 1.

[0332] <Production Examples of Toners 2 to 38>

[0333] Toners 2 to 38 were obtained in the same manner as in the Production Example of Toner 1, except that the toner particles and the external additive for toner were changed to those shown in Table 2.

[0334] [Table 2]

[0335]

[0336] In the table, the addition amount is in parts relative to 100 parts of toner particles.

[0337] <Production Example of Carrier 1>

[0338] - Magnetite 1 with a number average particle size of 0.30 μm (magnetization intensity of 65 Am in a magnetic field of 1000 / 4π (kA / m) 2 / kg).

[0339] - Magnetite 2 with a number average particle size of 0.50 μm (magnetization intensity of 65 Am in a magnetic field of 1000 / 4π (kA / m) 2 / kg).

[0340] Here, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added to 100 parts of each of the above materials, with high-speed mixing and stirring at 100° C. or higher in a container to treat each fine particle.

[0341] - Phenol: 10% by mass

[0342] -Formaldehyde solution: 6% by mass (40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water)

[0343] - Magnetite treated with the above-mentioned silane compound 1: 58% by mass

[0344] - Magnetite 2 treated with the above-mentioned silane compound: 26% by mass

[0345] Then, 100 parts of the above materials, 5 parts of 28% by mass ammonia solution, and 20 parts of water were placed in a flask. While stirring and mixing, the temperature was raised to 85°C within 30 minutes, and a polymerization reaction was carried out by maintaining the temperature for 3 hours to solidify the generated phenolic resin. The solidified phenolic resin was then cooled to 30°C, and then water was further added. The supernatant was then removed, and the precipitate was washed with water and subsequently air-dried. Next, the resulting product was dried at a temperature of 60°C under reduced pressure (below 5 mmHg) to obtain a magnetic body dispersed spherical carrier 1. The 50% particle size (D50) of the carrier 1 based on volume was 34.2 μm.

[0346] <Production Example of Two-Component Developer 1>

[0347] Here, 8.0 parts of Toner 1 is added to 92.0 parts of Carrier 1 , where they are mixed using a V-type blender (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain Two-Component Developer 1 .

[0348] <Production Examples of Two-Component Developers 2 to 38>

[0349] Two-component developers 2 to 38 were produced in the same manner as in the production example of the two-component developer 1, except that the toners were changed as given in Table 3 herein.

[0350] [Table 3]

[0351] Two-component developer No. Toner No. Carrier No. Two-component developer 1 Toner 1 Carrier 1 Two-component developer 2 Toner 2 Carrier 1 Two-component developer 3 Toner 3 Carrier 1 Two-component developer 4 Toner 4 Carrier 1 Two-component developer 5 Toner 5 Carrier 1 Two-component developer 6 Toner 6 Carrier 1 Two-component developer 7 Toner 7 Carrier 1 Two-component developer 8 Toner 8 Carrier 1 Two-component developer 9 Toner 9 Carrier 1 Two-component developer 10 Toner 10 Carrier 1 Two-component developer 11 Toner 11 Carrier 1 Two-component developer 12 Toner 12 Carrier 1 Two-component developer 13 Toner 13 Carrier 1 Two-component developer 14 Toner 14 Carrier 1 Two-component developer 15 Toner 15 Carrier 1 Two-component developer 16 Toner 16 Carrier 1 Two-component developer 17 Toner 17 Carrier 1 Two-component developer 18 Toner 18 Carrier 1 Two-component developer 19 Toner 19 Carrier 1 Two-component developer 20 Toner 20 Carrier 1 Two-component developer 21 Toner 21 Carrier 1 Two-component developer 22 Toner 22 Carrier 1 Two-component developer 23 Toner 23 Carrier 1 Two-component developer 24 Toner 24 Carrier 1 Two-component developer 25 Toner 25 Carrier 1 Two-component developer 26 Toner 26 Carrier 1 Two-component developer 27 Toner 27 Carrier 1 Two-component developer 28 Toner 28 Carrier 1 Two-component developer 29 Toner 29 Carrier 1 Two-component developer 30 Toner 30 Carrier 1 Two-component developer 31 Toner 31 Carrier 1 Two-component developer 32 Toner 32 Carrier 1 Two-component developer 33 Toner 33 Carrier 1 Two-component developer 34 Toner 34 Carrier 1 Two-component developer 35 Toner 35 Carrier 1 Two-component developer 36 Toner 36 Carrier 1 Two-component developer 37 Toner 37 Carrier 1 Two-component developer 38 Toner 38 Carrier 1

[0352] <Toner Evaluation Method>

[0353] (1) Measurement of image density changes

[0354] A Canon imagePress C800 full-color copier was used as an image forming apparatus. A two-component developer was placed in the cyan developing device of the image forming apparatus, and a toner was placed in the cyan toner container for evaluation described below. The apparatus was modified by installing a mechanism for discharging excess magnetic carrier contained in the developing device from the developing device. Plain paper GF-C081 (A4, basis weight 81.4 g / m2) was used as the evaluation paper. 2 , sold by Canon Marketing Japan Inc.).

[0355] The toner load on paper in the FFh image (solid image) was adjusted to 0.45 mg / cm 2 FFh is a value obtained by displaying 256 grayscales in hexadecimal, 00h is the first grayscale (white background portion) among the 256 grayscales, and FF is the 256th grayscale (solid portion) among the 256 grayscales. First, an image output test of 1000 images was performed at an image ratio of 1%. During the continuous passage of 1000 sheets of paper, the paper was passed under the same development conditions and transfer conditions as the first sheet (no calibration).

[0356] Thereafter, an image output test was conducted on 1,000 sheets at an image ratio of 80%. During the continuous passage of 1,000 sheets, the sheets were passed under the same development and transfer conditions as the first sheet (without calibration). The density of the 1,000th sheet of image printed at an image ratio of 1% was taken as the initial density, and the density of the 1,000th sheet of image printed at an image ratio of 80% was measured and evaluated.

[0357] The above test was conducted under a high temperature and high humidity environment (H / H; temperature 30°C, relative humidity 80%). Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite, Inc.), the initial density and the density of the 1000th image printed at an image ratio of 80% were measured, and the difference Δ between them was used to perform the evaluation according to the following criteria. Grades of C or higher were considered good. Table 4 shows the evaluation results.

[0358] Evaluation criteria: Image density difference Δ

[0359] A: less than 0.02

[0360] B: 0.02 or more and less than 0.05

[0361] C: 0.05 or more and less than 0.10

[0362] D: 0.10 or more and less than 0.15

[0363] E: 0.15 or more

[0364] (2) Evaluation method of transferability

[0365] A modified full-color copier manufactured by Canon Inc. (trade name: image RUNNER ADVANCE C5255) was used as the image forming apparatus. After an image output durability test in which 70,000 images were output in a high-temperature, high-humidity environment (30°C, 80% RH) (images with a print rate of 1%), solid images were output. Untransferred toner on the photosensitive member (photosensitive drum) during solid image formation was taped with a transparent polyester tape and then peeled off.

[0366] The peeled tape was attached to paper, and the density was measured using a spectroscopic densitometer (500 Series, X-Rite, Inc.). Alternatively, the density was also measured when only the tape was attached to the paper. The density difference Δ was calculated by subtracting the density value of the paper from the density value of the paper. This density difference Δ was evaluated based on the evaluation criteria shown below.

[0367] During the continuous output of 70,000 images, the images were output under the same development conditions and transfer conditions as the first image (without calibration). In the image output durability test of 70,000 copies, the copy paper CS-680 (A4 paper, basis weight: 68 g / m 2 , sold by Canon Marketing Japan Co., Ltd.) was used as a transfer material for evaluation. For the solid image after the output test, copy paper Multi-Purpose Paper: generally known as Boise paper (A4 paper, basis weight: 75 g / m 2 , sold by Canon USA). Rating was performed according to the following criteria. Grades C and above were determined to be good. Table 4 shows the evaluation results.

[0368] Evaluation criteria: Image density difference Δ

[0369] A: less than 0.02

[0370] B: 0.02 or more and less than 0.05

[0371] C: 0.05 or more and less than 0.10

[0372] D: 0.10 or more and less than 0.15

[0373] E: 0.15 or more

[0374] (3) Evaluation method of charge retention

[0375] The triboelectric charge of the toner is calculated by sucking and collecting the toner on the electrostatic latent image bearing member using a metal cylindrical tube and a cylindrical filter. Specifically, the triboelectric charge of the toner on the electrostatic latent image bearing member is measured using a Faraday cage. The Faraday cage is a coaxial double cylinder, and the inner and outer cylinders are insulated. When a charged body with a charge of Q is placed in the inner cylinder, it is as if a metal cylinder with a charge of Q exists due to electrostatic induction. The induced charge is measured with an electrometer (Keithley 6517A, manufactured by Keithley Co., Ltd.), and the (Q / M) obtained by dividing the charge Q (mC) by the mass M (kg) of the toner in the inner cylinder is taken as the triboelectric charge of the toner.

[0376] Triboelectric charge of toner (mC / kg) = Q / M

[0377] Evaluation image: Place a 2cm x 5cm FFh ​​image in the center of an A4 paper

[0378] First, an evaluation image was formed on a latent electrostatic image bearing member. Before transferring the image to an intermediate transfer body, the rotation of the latent electrostatic image bearing member was stopped, the toner on the latent electrostatic image bearing member was suctioned and collected using a cylindrical tube and a cylindrical filter, and the [initial Q / M] was measured. Subsequently, the evaluation machine, in which the developing device was arranged, was left for two weeks under an H / H environment, and then the same operation as before the leaving was performed, and the charge amount per unit mass Q / M (mC / kg) on ​​the latent electrostatic image bearing member after the leaving was measured. The initial Q / M per unit mass on the latent electrostatic image bearing member was taken as 100%, and the maintenance rate Q / M per unit mass on the latent electrostatic image bearing member after the leaving was calculated ([Q / M after leaving] / [initial Q / M]×100) and evaluated according to the following criteria. A grade of C or higher was determined to be good. Table 4 shows the evaluation results.

[0379] Evaluation Criteria

[0380] A: The maintenance rate is more than 98%

[0381] B: Maintenance rate is 95% or more and less than 98%

[0382] C: Maintenance rate is 90% or more and less than 95%

[0383] D: Maintenance rate is 85% or more and less than 90%

[0384] E: Maintenance rate is less than 85%

[0385] Evaluation results of Examples 1 to 33

[0386] Table 4 shows the evaluation results of Examples 1 to 33.

[0387] Evaluation results of Comparative Examples 1 to 5

[0388] Table 4 shows the evaluation results of Comparative Examples 1 to 5.

[0389] [Table 4]

[0390]

[0391] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments.The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

Claims

1. An external additive for toner, characterized in that: It includes particles of silicon polymer having siloxane bonds and Si-OC bonds, The external additive is surface-treated with at least one compound selected from the group consisting of alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, siloxane compounds, and silicone oil, wherein In the FT-IR spectrum of the external additive obtained by the ATR method, The maximum peak is at 1030 cm -1 to 1070cm -1 within the scope of When the spectrum is at 1015 cm -1 Up to 1025cm -1 The average intensity within the range is represented by A, and the -1 to 1095cm -1 When the average intensity within the range is represented by B, A and B satisfy the following formula (1): 0.55≤A / B≤1.50 ... (1). 2 . The external additive for toner according to claim 1 , wherein the external additive has a Young's modulus of 2000 MPa to 9000 MPa.

3. The external additive for toner according to claim 1 or 2, wherein in the FT-IR spectrum of the external additive, the maximum peak exists at 1040 cm -1 to 1055cm -1 within the range. 4 . The external additive for toner according to claim 1 , wherein the number average particle diameter of primary particles of the external additive is from 0.02 μm to 0.30 μm.

5. The external additive for toner according to claim 1 or 2, wherein in an FT-IR spectrum of the external additive obtained by an ATR method, the external additive has a wavelength of 1250 cm -1 Up to 1300cm -1 There is a peak in the range of . 6 . The external additive for toner according to claim 1 , wherein the external additive has an average circularity of 0.850 to 0.

950. 7 . The external additive for toner according to claim 1 , wherein the external additive has a yield point stress of 1,200 MPa to 10,000 MPa.

8. The external additive for toner according to claim 1 or 2, wherein the external additive is 29 In the graph obtained by Si-NMR measurement, when the total peak area attributable to the silicon polymer is represented by SA, the peak area attributable to the Q unit structure is represented by S4, the peak area attributable to the T unit structure is represented by S3, and the peak area attributable to the D unit structure is represented by S2, The SA, the S4, the S3, and the S2 satisfy the following formulas (I) to (III): 0.20≤S4 / SA≤0.60...(I) 0.00≤S3 / SA≤0.50...(II) 0.20≤S2 / SA≤0.70...(III). 9 . The toner external additive according to claim 1 , wherein the silicon polymer is a condensation polymer of at least one silicon compound selected from the group consisting of bifunctional silanes and at least one silicon compound selected from the group consisting of tetrafunctional silanes. 10 . The external additive for toner according to claim 1 , wherein the hydrophobicity of the external additive as determined by methanol titration is 50% to 60%.

11. A toner comprising toner particles and an external additive for toner, characterized in that: The toner particles include a binder resin, and The external additive for toner is the external additive for toner according to any one of claims 1 to 10. 12 . The toner according to claim 11 , wherein a content of the external additive for toner in the toner is 0.1 parts by mass to 20.0 parts by mass relative to 100 parts by mass of the toner particles.

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