External additive for toner and toner

Abstract

The present invention relates to an external additive for a toner and a toner. An external additive for a toner comprising a siloxane bond and a Si-R 1 Bonded silicon polymer particles, wherein R 1 represents an alkyl group having 1 to 6 carbon atoms, which is 29 In the graph obtained by Si-NMR measurement, the total peak area attributed to the external additive is represented by A, and the total peak area attributed to Si-R 1 In the case where the peak area of ​​the bond is represented by B, the following formula (1) is satisfied, and 29 In the graph obtained by Si-NMR measurement, when the total peak area attributable to the silicon polymer is represented by SA and the peak area attributable to the T unit structure is represented by S3, the following formula (2) is satisfied: 0.260≤B / A≤0.450...(1)0.00≤S3 / SA≤0.50...(2).

Description

Technical Field

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

[0002] In recent years, with the widespread use of full-color copiers of electronic photography, there is an increasing demand for electrophotographic toners that are suitable for high-speed printing and have environmental stability and long life. Conventionally, silica is widely known as an external additive for toners. Generally, examples in which silica obtained by a dry process or a wet process (sol-gel process) is surface-treated to improve hydrophobicity are reported. For example, Japanese Patent Application Publication No. 2007-099582 includes an example in which highly hydrophobic spherical sol-gel silica fine particles are added to toner base particles to improve the charging stability of the toner.

[0003] However, when outputting images in a high-temperature, high-humidity environment for extended periods, the silica present on the toner surface is susceptible to the effects of moisture within the image output device, which can alter the toner surface condition. Consequently, the toner's chargeability changes, and image density fluctuates. Furthermore, when outputting images after transitioning from a high-temperature, high-humidity environment to a low-humidity environment or a normal temperature and humidity environment, the silica present on the toner surface is also affected by humidity fluctuations, causing image density to vary. Therefore, there is still room for improvement in terms of toner charge stability in various image output environments.

[0004] Meanwhile, WO 2015 / 107961 and Japanese Patent Application Publication No. 2018-004949 describe examples in which polyalkylsilsesquioxane fine particles are added to toner base particles to improve the fluidity and charging stability of the toner. Furthermore, Japanese Patent Application Publication No. 2008-189545 describes an example of silica in which the number of highly hydrophilic silanol groups is reduced. Summary of the Invention

[0005] However, it has been found that the techniques described in the aforementioned patent documents are insufficient to suppress changes in the hygroscopicity of external additives when outputting images in a high-temperature, high-humidity environment or when outputting images under conditions of varying humidity. Therefore, there is room for improvement in toner charging stability, image density stability, and environmental stability.

[0006] The present disclosure provides an external additive for toner that has charging stability and can suppress fluctuations in image density even when an image is output in a high-temperature and high-humidity environment or when an image is output under conditions of varying humidity, and also provides a toner containing the external additive.

[0007] The present disclosure relates to an external additive for toner, comprising a toner having a siloxane bond and a Si-R 1 Bonded silicon polymer particles, wherein

[0008] R 1 represents an alkyl group having 1 to 6 carbon atoms,

[0009] Through external additives 29 In the graph obtained by Si-NMR measurement, the total peak area attributable to the external additive is represented by A, and the total peak area attributable to Si-R 1 When the peak area of ​​the bond is represented by B, A and B satisfy the following formula (1), and

[0010] Through external additives 29 In the graph obtained by Si-NMR measurement, when the total peak area attributed to the silicon polymer is represented by SA and the peak area attributed to the T unit structure is represented by S3, SA and S3 satisfy the following formula (2).

[0011] 0.260≤B / A≤0.450 ...(1)

[0012] 0.00≤S3 / SA≤0.50 ...(2)

[0013] The present disclosure can provide an external additive for toner that has charging stability and can suppress fluctuations in image density even when an image is output in a high-temperature and high-humidity environment or when an image is output under conditions of varying humidity, and also provide a toner containing the external additive.

[0014] Further features of the present invention will become apparent from the following description of exemplary embodiments. DETAILED DESCRIPTION

[0015] In this disclosure, unless otherwise specified, expressions such as "XX or greater and YY or less" and "XX to YY" indicating a numerical range include both 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 may be arbitrarily combined.

[0016] The present inventors believe that the above effect is exhibited according to the following mechanism. Typical sol-gel silica particles conventionally used as external additives for toners contain siloxane bonds (Si-O-Si) as a main component. Generally, since silanol groups are present at the ends of the sol-gel silica particles, unreacted residual silanol groups are present on the surface and inside the silica particles. Even if the residual silanol groups are trimethylsilylated by a coupling reaction with a silane compound or the like to increase hydrophobicity, it is not sufficient to suppress changes in chargeability during long-term use in a high-temperature, high-humidity environment.

[0017] As a result of diligent research by the present inventors, it was found that in the presence of a siloxane having a siloxane bond and a Si-R 1 In the case of external additives containing silicon polymers, the Si-R bond can be optimized by optimizing the internal Si-R bond of the external additive particles. 1 The above problems can be solved by adjusting the amount of (Si bonded to the alkyl group) present.

[0018] Regarding the mechanism, it is believed that the introduction of an alkyl group such as SiCH3 into the external additive particles increases the hydrophobicity of the external additive particles themselves and stabilizes the surface charge. As a result, it is speculated that changes in the toner charge level in high-temperature, high-humidity environments and changes in the toner charge level due to changes in humidity can be suppressed.

[0019] The present disclosure relates to an external additive for toner, comprising a toner having a siloxane bond and a Si-R 1 Bonded silicon polymer particles, wherein

[0020] R 1 represents an alkyl group having 1 to 6 carbon atoms,

[0021] In the case of toners with external additives 29 In the graph obtained by Si-NMR measurement, the total peak area attributable to the external additive for toner is represented by A, and the total peak area attributable to Si-R 1 When the peak area of ​​the bond is represented by B, A and B satisfy the following formula (1), and

[0022] In the process of using external additives in toner 29 In the graph obtained by Si-NMR measurement, when the total peak area attributed to the silicon polymer is represented by SA and the peak area attributed to the T unit structure is represented by S3, SA and S3 satisfy the following formula (2).

[0023] 0.260≤B / A≤0.450 ...(1)

[0024] 0.00≤S3 / SA≤0.50 ...(2)

[0025] exist 29 In Si-NMR, peaks are detected in different displacement regions depending on the structure of the functional group bonded to Si of the constituent compound of the silicon polymer. By using a standard sample to determine the position of each peak, the structure bonded to Si can be determined. In addition, the amount ratio of each constituent compound can be calculated from the obtained peak area. The ratio of the peak area of ​​the M unit structure (S1), D unit structure (S2), T unit structure (S3) and Q unit structure (S4) to the total peak area can be obtained by calculation.

[0026]

[0027] Ra, Rb, Rc, Rd, Re and Rf each independently represent an alkyl group having 1 to 6 (preferably 1 to 3, more preferably 1 or 2, and even more preferably 1) carbon atoms. 1 The ratio of the peak area B of the bond to the total peak area A (B / A) is the Si-R bond inside the external additive particles. 1 By satisfying the formula (1), the amount of the alkyl group present inside the external additive particles is optimized, and the environmental stability and charging stability of the toner can be improved.

[0028] 0.260≤B / A≤0.450 ...(1)

[0029] In Si-R 1 In, R 1 It represents an alkyl group having 1 to 6 (preferably 1 to 3, more preferably 1 or 2, still more preferably 1) carbon atoms.

[0030] When B / A is less than 0.260, the amount of alkyl groups present in the external additive particles is too small, and thus the effect of improving environmental stability and charge stability cannot be achieved. In addition, when B / A exceeds 0.450, the amount of siloxane bonds present in the external additive particles is relatively small, thereby reducing the firmness and stability of the particles.

[0031] Preferably, 0.280≤B / A≤0.450, more preferably 0.300≤B / A≤0.400, and further preferably 0.300≤B / A≤0.330. Within these ranges, the environmental stability and charging stability of the toner are further improved.

[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 by hydrolysis and polycondensation 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 by hydrolysis and polycondensation. Silane monomers such as bifunctional silane and tetrafunctional silane will be described below.

[0033] That is, the silicon polymer is preferably a condensation product 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, in a method for producing an external additive for toner, the above effects are achieved by adjusting the mixing ratio of monomers, solvent temperature during hydrolysis and condensation reactions, kind of catalyst, stirring time, pH of the solution, and the like.

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

[0036] The toner external additive contains 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.

[0037] The method for producing the silicon polymer particles is not particularly limited, and, for example, the silicon polymer particles can be obtained by adding a silane compound dropwise to water to induce a hydrolysis and condensation reaction mediated by a catalyst, and then 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 aqueous ammonia, sodium hydroxide, and potassium hydroxide, but are not limited thereto.

[0038] 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 the 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, hydrophobized spherical silicon polymer particles can be obtained by further mixing a hydrophobizing agent into the spherical silicon polymer particle dispersion.

[0039] In the first step, the silicon compound and the catalyst are brought into contact with each other by, for example, stirring or mixing in an aqueous solution of an acidic or alkaline substance serving as a catalyst dissolved in water. As the catalyst, known catalysts can be preferably used. Specifically, examples of suitable acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, and examples of suitable alkaline catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0040] The amount of the catalyst used can be appropriately adjusted depending on the types of the silicon compound and the catalyst. Preferably, the amount of the catalyst used is 1×10 -3The amount of the catalyst used is selected within the range of parts by mass to 1 part by mass.

[0041] 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. Meanwhile, 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.

[0042] The reaction temperature is not particularly limited, and the reaction can be carried out at room temperature or in a heated state, but the reaction is preferably carried out in a state where the temperature is maintained at 10 to 60° C. This is because in this case, a hydrolyzate is obtained in a short time and a partial condensation reaction of the generated hydrolyzate 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 obtained by compounding the silicon compound, acid, and water, and productivity.

[0043] 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.

[0044] 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.

[0045] The amount of the basic component used is an amount that allows the basic component to neutralize the acid and effectively serve as a catalyst for the polycondensation reaction; for example, in the case of using ammonia as the basic component, 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.

[0046] In the second step, in addition to the alkaline component and water, an organic solvent can be further used to prepare the alkaline aqueous medium. The organic solvent is not particularly limited as long as it is compatible with water, but an organic solvent that dissolves more than 10g of water per 100g at normal temperature and pressure is preferred herein.

[0047] 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.

[0048] Among the organic solvents listed above, alcoholic solvents such as methanol, ethanol, 2-propanol or butanol are preferred. In terms of hydrolysis and dehydration condensation reactions, it is more preferred to select the same alcohol as the alcohol generated by the desorption as the organic solvent.

[0049] The third step involves mixing the polycondensation reaction product obtained in the second step with an aqueous solution to initiate particle formation. Water (tap water or pure water, etc.) can be appropriately used as the aqueous solution herein, but water-compatible components such as salts, acids, bases, organic solvents, surfactants, or water-soluble polymers can be further added to the water. The temperature of the polycondensation reaction liquid and the aqueous solution during mixing is not particularly limited, and is appropriately selected within the range of 5 to 70°C, taking into account, for example, the composition of the solution and productivity.

[0050] As a method for recovering the silicon polymer particles, known methods can be used without particular limitation. For example, the floating powder can be scooped or filtered, but filtration is preferred because the operation involved is simple and convenient. The filtration method is not particularly limited, and known equipment for vacuum filtration, centrifugal filtration, or pressure filtration can be selected herein. The filter paper, filter, or filter cloth used for filtration is not particularly limited as long as it is industrially available and can be appropriately selected depending on the equipment used.

[0051] The hydrophobicity of the silicone polymer particles can be adjusted by treating the surface of the silicone polymer particles using a known means such as a silane coupling agent or silicone oil.

[0052] The monomer used can be appropriately selected depending on compatibility with the solvent and catalyst, hydrolyzability, etc., but the tetrafunctional silane is preferably tetraethoxysilane. The difunctional silane is preferably dimethyldimethoxysilane.

[0053] 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).

[0054]

[0055] In formula (2), R 2 、R 3 、R 4 and R 5R independently represents an alkyl group having 1 to 6 (preferably 1 to 3, and more preferably 1 or 2) carbon atoms, 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 them is a reactive group.

[0056] R 2 、R 3 、R 4 and R 5 Independently preferred are alkyl groups having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms, and more preferably 1 or 2 carbon atoms), or alkoxy groups (preferably having 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms).

[0057] In order to obtain silicon polymer particles, a silicon compound having four reactive groups in one molecule of formula (2) (tetrafunctional silane) and R in formula (2) can be used. 2 is an alkyl or phenyl group and has three reactive groups (R 3 、R 4 、R 5 ) organic silicon compound (trifunctional silane), 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 R in formula (2) 2 、R 3 、R 4 Each is an alkyl group or a phenyl group and has one reactive group (R 5 ) of an organosilicon compound (monofunctional silane).

[0058] These reactive groups are hydrolyzed, addition-polymerized, and condensed to form a cross-linked structure, and silicon polymer particles can be obtained. 3 、R 4 and R 5 The hydrolysis, addition polymerization and condensation polymerization can be controlled by reaction temperature, reaction time, reaction solvent and pH.

[0059] The tetrafunctional silane can be exemplified by tetramethoxysilane, tetraethoxysilane, and tetraisocyanatosilane.

[0060] Examples of the trifunctional silane include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, and methylethoxysilane. 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.

[0061] The difunctional 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.

[0062] Examples of the monofunctional silane include 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.

[0063] The silicon polymer contained in the external additive for toner preferably has a siloxane bond, Si-R 1 bond and Si-OR 2 Key. In the process of using external additives in toner 29In the graph obtained by Si-NMR measurement, in the graph attributed to Si-OR 2 When the peak area of ​​is represented by C, it preferably satisfies the following formula (3).

[0064] 0.050≤(C / A) / (B / A)≤0.180 ...(3)

[0065] R 2 represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.

[0066] Within the above range, the hydrophobicity Si-R inside the external additive particles is optimized. 1 The ratio of the amount of the hydrophilic silanol group to the amount of the hydrophilic silanol group is 0.060, and the overcharging suppression effect is exhibited in a low-humidity environment. That is, this range is preferred from the perspectives of the environmental stability and charging stability of the toner. More preferably, 0.060 ≤ (C / A) / (B / A) ≤ 0.150, and even more preferably 0.075 ≤ (C / A) / (B / A) ≤ 0.085.

[0067] (C / A) / (B / A) can be controlled by the selection of the silicon compound, the mixing ratio of the silicon compound, and the hydrolysis and condensation conditions. For example, (C / A) / (B / A) can be increased by increasing the mixing ratio of the tetrafunctional silane, lowering the temperature during the condensation reaction, and lowering the temperature during the hydrolysis period, and (C / A) / (B / A) can be decreased by increasing the mixing ratio of the difunctional 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 period.

[0068] 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, it is easier to uniformly coat the toner particles with the external additive. Furthermore, since stress on the toner is suppressed, the effect of charge stability can be easily achieved.

[0069] 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, even when a large number of low-density images are output over a long period of time in harsh environments such as high temperature and high humidity. Therefore, the external additive particles are less likely to become embedded in the toner particle surface. Furthermore, when the number average particle size is 0.30 μm or smaller, it becomes difficult for the external additive particles to separate 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.

[0070] The surface of the toner external additive is preferably treated with a hydrophobic agent. That is, the particles of the toner external additive are preferably silicon polymer particles surface-treated with a hydrophobic agent. The hydrophobic agent is not particularly limited, but is preferably an organosilicon compound.

[0071] 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, and siloxane compounds such as octamethylcyclotetrasiloxane, silicone oil, silicone varnish, and the like.

[0072] By hydrophobizing the surface of the external additive particles, changes in the toner charge level in 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 perspectives of environmental stability and charge stability, surface-treatment with an alkylsilazane compound is more preferred.

[0073] From the viewpoint of charging stability, the hydrophobicity of the external additive for toner, as obtained by methanol titration, is preferably from 40% to 80%, more preferably from 50% to 60%, and further preferably from 50% to 55%.

[0074] In the process of using external additives in toner 29 In the graph obtained by Si-NMR measurement, 0.00≤S3 / SA≤0.50, where SA is the total peak area attributed to the silicon polymer and S3 is the peak area attributed to the T unit structure. 1 The ratio of the amount of the silanol group to the amount of the silanol group is optimized, and the environmental stability and charging stability of the toner are further improved. In addition, 0.00≤S3 / SA≤0.40 is preferable, and 0.00≤S3 / SA≤0.20 is more preferable.

[0075] 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, the following formulae (I) to (III) are preferably satisfied.

[0076] 0.20≤S4 / SA≤0.60 ...(I)

[0077] 0.00≤S3 / SA≤0.50 ...(II)

[0078] 0.20≤S2 / SA≤0.70 ...(III)

[0079] In the case where formulae (I) to (III) are satisfied, when the toner is subjected to stress from a member such as a carrier, it is possible to prevent external additive particles from being buried in the toner particle surface and to prevent the external additive particles themselves from being broken.

[0080] Furthermore, more preferably 0.30≤S4 / SA≤0.50, 0≤S3 / SA≤0.10 and 0.50≤S2 / SA≤0.70. Within these ranges, Si-R such as Si-CH3 in the external additive particles 1 The ratio of the amount of the silanol group to the amount of the silanol group is optimal, which is more preferred from the perspective of environmental stability and charging stability of the toner. S4 / SA, S3 / SA and S2 / SA can be controlled by the selection of the silicon compound, the mixing ratio of the silicon compound, and the hydrolysis and condensation conditions.

[0081] By using external additives in toner 29 The ratio of the peak area attributable to the siloxane bond in the total peak area attributable to the silicon polymer calculated from the graph obtained by Si-NMR measurement is preferably 60.0% to 85.0%, and more preferably 63.0% to 68.0%. When the ratio is within the above range, the Si-R such as Si-CH3 inside the external additive particles 1 The area ratio is optimal with respect to the amount of the silanol group present, and the chargeability in a high-humidity environment is improved, which is preferred. The area ratio can be controlled by the selection of the silicon compound, the mixing ratio of the silicon compound, and the hydrolysis and condensation conditions.

[0082] From the viewpoint of durable stability and charging stability of the toner, the average circularity of the external additive for toner is preferably 0.85 to 0.95, and more preferably 0.88 to 0.93. The average circularity can be controlled by the mixing ratio of the monomers and the condensation conditions.

[0083] The toner includes toner particles containing a binder resin and an external additive for the toner, wherein the external additive for the toner is the above-mentioned external additive for the toner. From the perspective of charge stability, the content of the external additive for the 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.

[0084] 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 can be improved, even when a large number of images with low print density are output for a long period of time in a harsh environment such as a high-temperature, high-humidity environment. 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 images with high print density are output for a long period of time.

[0085] <Binder Resin>

[0086] The binder resin for toner is not particularly limited, and for example, the following polymers can be used. For example, monomers of styrene and substituted styrenes, such as polystyrene, polyparachlorostyrene, and polyvinyltoluene, styrene-based copolymers, such as styrene-parachlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylate copolymers, styrene-methacrylate copolymers, styrene-methacrylate α-chloromethyl ester copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers, and polyvinyl chloride, phenolic resins, 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, coumarone-indene resins, and petroleum resins can be used. Among them, polyester resins are preferred from the perspective of durable stability and charge stability.

[0087] Furthermore, from the viewpoint of environmental stability and charging stability, it is preferred that the acid value of the polyester resin be 0.5 mg KOH / g to 40 mg KOH / g. 1 interact with each other, and the toner chargeability in a high-humidity environment can be further improved.The acid value is more preferably from 1 mg KOH / g to 20 mg KOH / g, and even more preferably from 1 mg KOH / g to 15 mg KOH / g.

[0088] <Colorant>

[0089] Colorants can be used in toner particles. A colorant can also be included in toner particles. Examples of colorants are listed below. Examples of black colorants include carbon black and black obtained by toning a mixture of a yellow colorant, a magenta colorant, and a cyan colorant. A pigment can be used alone as a colorant, but from the perspective of image quality for full-color images, it is preferred to use a dye and a pigment together to improve vividness.

[0090] 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; and CI Vat Red 1, 2, 10, 13, 15, 23, 29, and 35.

[0091] 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.

[0092] 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 phthalimidomethyl groups substituted on the phthalocyanine skeleton. Examples of cyan dyes include CI Solvent Blue 70.

[0093] 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.

[0094] <Wax>

[0095] 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 polyethylene oxide wax and its block copolymers; waxes primarily composed of fatty acid esters such as carnauba wax; and partially or completely deoxygenated fatty acid esters such as deoxygenated carnauba wax.

[0096] Other examples include the following: saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brazilic acid, eleostearic acid, and stearidonic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnauba alcohol, seryl alcohol, and myristic alcohol; 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 alcohols, behenyl alcohol, carnauba alcohol, seryl alcohol, and myristic alcohol; fatty acid amides such as linoleamide, oleamide, and lauramide; saturated fatty acid bisamides such as methylene bisstearamide, ethylene biscapramamide, ethylene bislauramamide, and hexamethylene bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, and linoleamide. The binder resin includes: bis(acrylic acid)amide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearamide 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.

[0097] <Charge Control Agent>

[0098] The toner particles may contain 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, produce toner particles with a fast charging speed, and can stably maintain a certain charge amount.

[0099] Examples of negatively charged charge control agents include salicylic acid metal compounds, naphthoic 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.

[0100] Examples of positively charged charge control agents include quaternary ammonium salts, polymer compounds having a quaternary ammonium salt in a side chain, guanidine compounds, and imidazole compounds. The charge control agent may be added to the toner particles internally or externally. The amount of the charge control agent added is preferably 0.2 to 10 parts by mass per 100 parts by mass of the binder resin.

[0101] <Inorganic fine particles>

[0102] If desired, in addition to the above-mentioned external additives for toners, the toner may also contain other inorganic fine particles. 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.

[0103] 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 within the above range may be used in combination with an external additive for toner to achieve both improvement in fluidity and stabilization of durability.

[0104] 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 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.

[0105] <Developer>

[0106] Although the toner can be used as a single-component developer, 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 over a long period of time. In other words, in a two-component developer containing a toner and a magnetic carrier, the toner is preferably the above-mentioned toner.

[0107] The following substances can be used as the magnetic carrier: for example, iron oxide, unoxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium and rare earth particles, alloy particles thereof, and oxide particles thereof; magnetic substances such as ferrite; magnetic substance-dispersed resin carriers (so-called resin carriers) comprising a magnetic substance and a binder resin that holds the magnetic substance 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.

[0108] <Method for Producing Toner Particles>

[0109] The method for producing the toner particles is not particularly limited, and a known production method such as a suspension polymerization method, an emulsion aggregation method, a melt kneading method, or a dissolution suspension method can be employed. A toner can then be obtained by mixing the above toner external additive and, if necessary, other external additives with the obtained toner particles.

[0110] The mixing of the toner particles and the external additive can be accomplished using a mixing device such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a MechanoHybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0111] The following explains how to measure various physical properties.

[0112] <Separation of External Additive Particles and Toner Particles from Toner>

[0113] The physical properties can also be measured by using an external additive separated from the toner by 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 thick solution. A total of 31g of sucrose thick solution and 6mL of Contaminone N (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments; pH 7 and containing a nonionic surfactant, an anionic surfactant and an organic detergent; 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 spatula or the like.

[0114] The centrifuge tube was shaken for 20 minutes at 350 reciprocating strokes 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.

[0115] After centrifugation, the toner is present in the top layer of the glass tube, and the toner external additive is present in the aqueous solution on 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. If necessary, the centrifugation is repeated, and after sufficient separation, the dispersion is dried and the toner external additive is collected. When multiple toner external additives are added, the toner external additives can be separated by centrifugation or other methods.

[0116] <Method for Measuring the Number Average Particle Diameter of Primary Particles of External Additive Particles for Toner>

[0117] The number average particle size of the primary particles of the external additive particles for toner is measured according to the centrifugal sedimentation method. Specifically, 0.01g of dried external additive particles are placed in a 25ml glass vial, and 0.2g of 5% Triton solution and 19.8g of RO water are added thereto to produce a solution. Next, the probe of the ultrasonic disperser (the tip in the leading end) is immersed in the solution and ultrasonically dispersed for 15 minutes with an output power of 20W. As a result, a dispersion liquid is obtained. Next, using this dispersion liquid, the number average particle size of the primary particles is measured by means of a centrifugal sedimentation particle size distribution measuring device DC24000 manufactured by CPS Instruments Inc. The disc rotation speed is set to 18000rpm, and the true density is set to 1.3g / cm 3Before the measurement, the device was calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0118] <Method for measuring the acid value of resin>

[0119] The acid value is the number of mg of potassium hydroxide required to neutralize acid components such as free fatty acids and resin acids contained in 1 g of a sample. The acid value is measured in the following manner according to JIS-K0070-1992.

[0120] (1) Reagents

[0121] A total of 1.0 g of phenolphthalein was dissolved in 90 mL of ethanol (95% by volume), ion-exchanged water was added to make 100 mL and a phenolphthalein solution was obtained.

[0122] The 7g special grade potassium hydroxide that amounts to is dissolved in 5mL water and adds ethanol (95 volume %) to reach 1L.Solution is placed in alkali-resistant container to avoid contacting with carbon dioxide, it was left standstill 3 days, then filtered to obtain potassium hydroxide solution.The potassium hydroxide solution that obtains is kept in alkali-resistant container.To amount to 25mL 0.1mol / L hydrochloric acid is placed in triangular flask, adds several drops of phenolphthalein solution, titrates with potassium hydroxide solution, and obtains the coefficient of potassium hydroxide solution by the amount of neutralization required potassium hydroxide solution.Prepare employed 0.1mol / L hydrochloric acid according to JIS K 8001-1998.

[0123] (2) Operation

[0124] (A) This test

[0125] A total of 2.0 g of pulverized sample was accurately weighed into a 200 mL conical flask, 100 mL of a mixed solution of toluene / ethanol (2:1) was added, and dissolved over 5 h. A few drops of phenolphthalein solution were then added as an indicator, and titrated using potassium hydroxide solution. The endpoint of the titration was when the light red color of the indicator lasted for approximately 30 seconds.

[0126] (B) Blank test

[0127] The same titration as in the above operation was performed except that no sample was used (ie, only a mixed solution of toluene / ethanol (2:1) was used).

[0128] (3) The obtained results were substituted into the following formula to calculate the acid value.

[0129] A=[(CB)×f×5.61] / S

[0130] Here, A: acid value (mg KOH / g), B: amount of potassium hydroxide solution added in the blank test (mL), C: amount of potassium hydroxide solution added in this test (mL), f: potassium hydroxide solution coefficient, and S: mass of the sample (g).

[0131] <Measurement of Acid Value of Toner-Derived Polyester Resin>

[0132] The following method can be used to measure the acid value of the polyester resin in the toner. The polyester resin is separated from the toner by the following method and the acid value is measured. The toner is dissolved in tetrahydrofuran (THF), and the solvent is distilled out from the soluble component obtained under reduced pressure to obtain the tetrahydrofuran (THF) soluble component of the toner. The tetrahydrofuran (THF) soluble component of the toner obtained is dissolved in chloroform to prepare a sample solution with a concentration of 25 mg / ml. A total of 3.5 mL of the sample solution obtained is injected into the following equipment, and the component with a molecular weight of 2000 or more is separated as the resin component under the following conditions.

[0133] Preparative GPC equipment: Preparative HPLC LC-980 manufactured by Nippon Analytical Industry Co., Ltd.

[0134] Separation columns: JAIGEL 3H, JAIGEL 5H (manufactured by Nippon Analytical Industry Co., Ltd.)

[0135] Eluent: chloroform

[0136] Flow rate: 3.5ml / min

[0137] After separating the high molecular weight component derived from the resin, the solvent was distilled off under reduced pressure, and then dried under reduced pressure at 90°C for 24 hours. The above operation was repeated until about 2.0 g of the resin component was obtained. Using the obtained sample, the acid value was measured according to the above process.

[0138] <Method for measuring weight-average particle diameter (D4) of toner particles>

[0139] The weight-average particle diameter (D4) of the toner particles is determined by the following method: measurement is carried out in a channel with an effective measurement channel number of 25,000, using a "Coulter Counter Multisizer 3" (registered trademark, Beckman Coulter, Inc.) (a precision particle size distribution measuring instrument that operates based on the pore resistance method and is equipped with a 100 μm orifice tube) and using attached dedicated software for setting measurement conditions and analyzing measurement data, i.e., "Beckman Coulter Multisizer 3, Version 3.51" (Beckman Coulter, Inc.) to perform analysis of the measurement data.

[0140] The electrolyte aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to provide a concentration of about 1 mass %, and, for example, "ISOTON II" (Beckman Coulter, Inc.) can be used. Prior to measurement and analysis, dedicated software is set as follows.

[0141] 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. Furthermore, the current was set to 1,600 μA, the gain to 2, the electrolyte solution to ISOTON II, and the post-measurement nozzle flush was enabled.

[0142] In the dedicated software's "Pulse to Particle Size Conversion Settings" interface, set the element spacing to logarithmic particle size, the particle size element to 256 particle size elements, and the particle size range to 2μm to 60μm. The specific measurement process is as follows.

[0143] (1) Pour approximately 200 mL of the above electrolyte aqueous solution into a 250 mL round-bottom glass beaker dedicated to the Multisizer 3, place it on the sample stage, and stir counterclockwise at 24 revolutions per second with a stirring rod. Use the "Bore Tube Rinse" function in the dedicated software to preliminarily remove dirt and bubbles from the nozzle.

[0144] (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 containing a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times (by mass) with deionized water was added thereto as a dispersant.

[0145] (3) A predetermined amount of deionized water was introduced into a water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (NikkakiBios Co., Ltd.) having a power output of 120 W and equipped with two oscillators (oscillation frequency = 50 kHz) configured to be 180° phase-shifted, and about 2 mL of Contaminon N was added to the water tank.

[0146] (4) The beaker described in (2) is set in the beaker fixing hole on the ultrasonic disperser, and the ultrasonic disperser is started. The height position of the beaker is adjusted to maximize the resonance state of the liquid surface of the aqueous electrolyte solution in the beaker.

[0147] (5) While ultrasonic waves are being irradiated on the electrolyte aqueous solution in the beaker set up according to (4), approximately 10 mg of the toner particles are added in small portions to the electrolyte aqueous solution and dispersed. The ultrasonic dispersion treatment is continued for an additional 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately controlled to 10°C to 40°C.

[0148] (6) Using a pipette, add the electrolyte aqueous solution containing the dispersed toner prepared in (5) dropwise to the round-bottom beaker set in the sample stage as described in (1), adjusting the concentration to provide a measurement concentration of approximately 5%. Then, measurement is performed until the number of measured particles reaches 50,000.

[0149] (7) Analyze the measurement data using the dedicated software included with the instrument 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).

[0150] <Method for Measuring Average Circularity of Toner External Additive Particles, Toner Particles, and Toner>

[0151] The average circularity is a simple method for quantitatively expressing the shape of particles. Particles with a circle-equivalent diameter ranging from 0.01 μm to 400 μm are measured using the FPIA-3000 flow particle image analyzer manufactured by Sysmex Corporation. The circularity of the measured particles is calculated using 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 measured is 5,000.

[0152] Circularity a=L0 / L

[0153] (In the formula, 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 are 0.3 μm×0.3 μm)).

[0154] <Method for Measuring Hydrophobicity of External Additive for Toner>

[0155] The hydrophobicity of the toner external additive particles 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 the 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.

[0156] Complete wetting is determined by whether the toner external additive floating on the water surface is completely immersed in the liquid and suspended in the liquid. The volume percentage of methanol in the total volume 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.

[0157] <Through solid state 29 Method for measuring the abundance ratio, B / A, and (C / A) / (B / A) of the constituent compounds of external additives for toners by Si-NMR>

[0158] In solid state 29 In Si-NMR, peaks are detected in shift regions that vary depending on the structure of the Si-bonded functional groups in the compounds that constitute the toner external additive. By using standard samples to determine the positions of each peak, the Si-bonded structure can be identified. 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, the T unit structure, and the D unit structure to the total peak area can be calculated.

[0159] Specifically, solid-state 29 The measurement conditions of Si-NMR are as follows.

[0160] Equipment: JNM-ECX5002 (JEOL RESONANCE)

[0161] Temperature: Room temperature

[0162] Measurement method: DDMAS method 29 Si 45°

[0163] Sample tube: Zirconia, diameter 3.2mm

[0164] Sample: Filled in sample tube in powder form

[0165] Sample rotation speed: 10kHz

[0166] Relaxation delay: 180s

[0167] Scans: 2000

[0168] After measurement, peaks are separated into M unit structure, D unit structure, T unit structure, and Q unit structure by curve fitting of a sample or a plurality of silane components having different substituents and bonding groups of an external additive for toner, and each peak area is calculated.

[0169] Curve fitting was performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series) (software for 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 was performed for each component so that the difference (synthetic peak difference) between the synthetic peak obtained by combining the peaks obtained by curve fitting and the peak of the measurement result was minimized.

[0170] M unit structure: (Ra)(Rb)(Rc)SiO 1 / 2 (S1)

[0171] D unit structure: (Rd)(Re)Si(O 1 / 2 )2 (S2)

[0172] T unit structure: RfSi(O 1 / 2 )3 (S3)

[0173] Q unit structure: Si(O 1 / 2 )4 (S4)

[0174] (S1+S2+S3+S4)=SA.

[0175] In formulas (S1), (S2) and (S3), Ra, Rb, Rc, Rd, Re and Rf are each an organic group (e.g., an alkyl group) or a halogen atom such as a hydrocarbon group having 1 to 6 carbon atoms bonded to silicon. 13 C-NMR and 1 The results of H-NMR measurements are consistent with 29 The results of Si-NMR measurements were used for identification. From the SA, S2, S3, and S4 thus obtained, S2 / SA, S3 / SA, and S4 / SA were calculated.

[0176] (B / A calculation method)

[0177] By solid state 29 The Si-NMR pattern was obtained and the (Si-R 1 ) peak area. R 1 As described above and represents an alkyl group having 1 to 6 carbon atoms.

[0178] With (Si-R 1 ) is represented by the peak area of ​​the Q4 unit structure of (Si-R 1 ) is represented by the peak area of ​​the Q3 unit structure of (Si-R 1 ) is represented by the peak area of ​​the Q2 unit structure of S42, and has (Si-R 1 ) is represented by the peak area of ​​the Q1 unit structure.

[0179] With (Si-R 1 ) is represented by the peak area of ​​the T3 unit structure of (Si-R 1 ) is represented by the peak area of ​​the T2 unit structure of S32, and has (Si-R 1 ) is represented by the peak area of ​​the T1 unit structure.

[0180] With (Si-R 1 ) is represented by the peak area of ​​the D2 unit structure of (Si-R 1 ) is represented by the peak area of ​​the D1 unit structure.

[0181] With (Si-R 1 ) is represented by S11.

[0182] At this time, the Si-R in each unit structure is calculated as follows 1 The peak area ratio.

[0183] Si-R belonging to the Q unit structure 1Peak area ratio QB = (S44 / S4) × 0 + (S43 / S4) × 0 + (S42 / S4) × 0 + (S41 / S4) × 0

[0184] Si-R belonging to the T unit structure 1 Peak area ratio TB = (S33 / S3) × 1 / 4 + (S32 / S3) × 1 / 4 + (S31 / S3) × 1 / 4

[0185] Si-R belonging to the D unit structure 1 Peak area ratio DB = (S22 / S2) × 1 / 2 + (S21 / S2) × 1 / 2

[0186] Si-R belonging to the M unit structure 1 Peak area ratio MB = S11 / S1×3 / 4

[0187] The structural units of silicon polymers are classified into M units (monofunctional), D units (difunctional), T units (trifunctional) and Q units (tetrafunctional) according to the number of functional groups. In the present disclosure, the difference in the degree of condensation in each unit is expressed as D1 unit, D2 unit, T1 unit, T2 unit and T3 unit according to the number of cross-linked oxygen atoms. That is, the numbers after letters such as D and T represent the number of cross-linked oxygen atoms that form siloxane bonds. For example, a T3 unit means that all three functional groups are condensed to participate in a siloxane bond. In addition, a T2 unit means that two of the three functional groups are condensed to participate in a siloxane bond, and one functional group is not condensed.

[0188] Q unit structure

[0189] Q4: -105ppm to -115ppm

[0190] Q3: -95ppm to -104ppm

[0191] Q2: -85ppm to -94ppm

[0192] Q1: -75ppm to -84ppm

[0193] T unit structure

[0194] T3: -60ppm to -70ppm

[0195] T2: -50ppm to -59ppm

[0196] T1: -40ppm to -49ppm

[0197] D unit structure

[0198] D2: -15ppm to -25ppm

[0199] D1: -10ppm to -14ppm

[0200] M unit structure

[0201] M1: -5ppm to -9ppm

[0202] From the above formula, we can calculate B / A=QB+TB+DB+MB.

[0203] (Calculation Methods for C / A and (C / A) / (B / A))

[0204] By solid state 29 The Si-NMR spectrum was used to calculate the unreacted groups (Si-OR 2 ) peak area. R 2 represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.

[0205] With unreacted groups (Si-OR 2 ) is represented by the peak area of ​​the Q4 unit structure with unreacted groups (Si-OR 2 ) is represented by the peak area of ​​the Q3 unit structure with unreacted groups (Si-OR 2 ) is represented by the peak area of ​​the Q2 unit structure of S42, and has an unreacted group (Si-OR 2 ) is represented by the peak area of ​​the Q1 unit structure.

[0206] With unreacted groups (Si-OR 2 ) is represented by the peak area of ​​the T3 unit structure with unreacted groups (Si-OR 2 ) is represented by the peak area of ​​the T2 unit structure of S32, and has an unreacted group (Si-OR 2 ) is represented by the peak area of ​​the T1 unit structure.

[0207] With unreacted groups (Si-OR 2 ) is represented by the peak area of ​​the D2 unit structure, and has an unreacted group (Si-OR 2 ) is represented by the peak area of ​​the D1 unit structure.

[0208] With unreacted groups (Si-OR 2 ) is represented by S11.

[0209] At this time, the Si-OR in each unit structure is calculated as follows 2 The peak area ratio.

[0210] Si-OR belonging to the Q unit structure 2Peak area ratio QC = (S44 / S4) × 0 + (S43 / S4) × 1 / 4 + (S42 / S4) × 1 / 2 + (S41 / S4) × 3 / 4,

[0211] Si-OR belonging to the T unit structure 2 Peak area ratio TC = (S33 / S3) × 0 + (S32 / S3) × 1 / 4 + (S31 / S3) × 1 / 2,

[0212] Si-OR belonging to the D unit structure 2 Peak area ratio DC = (S22 / S2) × 0 + (S21 / S2) × 1 / 4,

[0213] Si-OR belonging to the M unit structure 2 The peak area ratio MC=S11 / S1×0

[0214] Q unit structure

[0215] Q4: -105ppm to -115ppm

[0216] Q3: -95ppm to -104ppm

[0217] Q2: -85ppm to -94ppm

[0218] Q1: -75ppm to -84ppm

[0219] T unit structure

[0220] T3: -60ppm to -70ppm

[0221] T2: -50ppm to -59ppm

[0222] T1: -40ppm to -49ppm

[0223] D unit structure

[0224] D2: -15ppm to -25ppm

[0225] D1: -10ppm to -14ppm

[0226] M unit structure

[0227] M1: -5ppm to -9ppm

[0228] C / A = QC + TC + DC + MC is calculated from the above formula. Also, (C / A) / (B / A) is calculated from B / A calculated above.

[0229] (Ratio of peak area attributable to siloxane bond)

[0230] By solid state 29 From the chart obtained by Si-NMR, the ratio of the peak area attributable to the siloxane bond to the total peak area attributable to the silicon polymer was calculated by the following method.

[0231] The peak area attributable to the Q4 unit structure having a siloxane bond is represented by p44, the peak area attributable to the Q3 unit structure having a siloxane bond is represented by p43, the peak area attributable to the Q2 unit structure having a siloxane bond is represented by p42, and the peak area attributable to the Q1 unit structure having a siloxane bond is represented by p41.

[0232] The peak area attributed to the T3 unit structure having a siloxane bond is represented by p33, the peak area attributed to the T2 unit structure having a siloxane bond is represented by p32, and the peak area attributed to the T1 unit structure having a siloxane bond is represented by p31.

[0233] The peak area attributable to the D2 unit structure having a siloxane bond is represented by p22, and the peak area attributable to the D1 unit structure having a siloxane bond is represented by p21.

[0234] The peak area attributable to the M1 unit structure having a siloxane bond is represented by p11.

[0235] At this time, the peak area ratio attributable to the siloxane bond in each unit structure was calculated as follows.

[0236] The peak area ratio of the siloxane bond attributable to the Q unit structure Qp = (p44 / S4) + (p43 / S4) × 3 / 4 + (p42 / S4) × 1 / 2 + (p41 / S4) × 1 / 4

[0237] The peak area ratio of the siloxane bond attributable to the T unit structure is Tp = (p33 / S3) × 3 / 4 + (p32 / S3) × 1 / 2 + (p31 / S3) × 1 / 4

[0238] The peak area ratio of the siloxane bond attributable to the D unit structure Dp = (p22 / S2) × 1 / 2 + (p21 / S2) × 1 / 2

[0239] The peak area ratio of the siloxane bond attributable to the M unit structure is Mp = p11 / S1×1 / 4

[0240] Based on the above, the area ratio of the peak attributed to the siloxane bond = Qp + Tp + Dp + Mp is calculated.

[0241] <Measuring Method for Surface Treatment Agent for Toner External Additive>

[0242] 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.

[0243] Equipment: GC6890A (manufactured by Agilent Technologies, Inc.), pyrolyzer (manufactured by Japan Analytical Industry Co., Ltd.)

[0244] Column: HP-5ms 30m

[0245] Pyrolysis temperature: 590℃

[0246] By determining the position of each peak of a spectrum obtained by measurement using a standard sample, the surface treatment agent used for the external additive for toner is determined.

[0247] Example

[0248] 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 language "parts" in the following formulations refer to parts by mass in all cases.

[0249] <Production Example of Toner External Additive Particles 1>

[0250] 1. Hydrolysis process

[0251] A total of 43.2 g of RO water and 0.008 g of acetic acid as a catalyst were placed in a 200 ml beaker and stirred at 45° C. 27.2 g of tetraethoxysilane and 27.2 g of dimethyldimethoxysilane were added thereto, followed by stirring for 1.5 hours to obtain a raw material solution.

[0252] 2. Polycondensation process

[0253] 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 mixture after the addition of the raw material solution was stirred at 30°C for 1.5 hours to carry out a polycondensation reaction and obtain a polycondensation reaction liquid.

[0254] 3. Particle formation process

[0255] 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 silicone polymer particles having siloxane bonds was obtained.

[0256] 4. Hydrophobization process

[0257] A total of 27.1 g of hexamethyldisilazane (a hydrophobic agent) was added to the dispersion containing silicone polymer particles having siloxane bonds obtained in "3. Particle Formation Step," followed by stirring at 60°C for 2.5 hours. After the dispersion was allowed to stand for 5 minutes, the powder precipitated at the bottom of the solution was recovered by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain Toner External Additive Particles 1. The number average primary particle size of the obtained Toner External Additive Particles 1 was 0.12 μm. Table 1 shows the physical properties of Toner External Additive Particles 1.

[0258] <Production Example of Toner External Additive Particles 2>

[0259] 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.

[0260] <Production Example of Toner External Additive Particles 3>

[0261] 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.

[0262] <Production Example of Toner External Additive Particles 4>

[0263] 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% aqueous ammonia 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.

[0264] <Production Example of Toner External Additive Particles 5>

[0265] 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% aqueous ammonia 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.

[0266] <Production Example of Toner External Additive Particles 6>

[0267] 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 the amount of RO water, methanol, and 25% ammonia water in the polycondensation step were changed to 98.8 g, 310.0 g, and 1.5 g, respectively. Table 1 shows the physical properties of the obtained Toner External Additive Particles 6.

[0268] <Production Example of Toner External Additive Particles 7>

[0269] 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 the amount of RO water, methanol, and 25% ammonia water in the polycondensation step were changed to 58.8 g, 350.0 g, and 2.5 g, respectively. Table 1 shows the physical properties of the obtained Toner External Additive Particles 7.

[0270] <Production Example of Toner External Additive Particles 8>

[0271] Toner External Additive Particles 8 were obtained in the same manner as in the production example of Toner External Additive Particles 1 except that 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 h. Table 1 shows the physical properties of the obtained Toner External Additive Particles 8.

[0272] <Production Example of Toner External Additive Particles 9>

[0273] Toner External Additive Particles 9 were obtained in the same manner as in the production example of Toner External Additive Particles 1 except that 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 9.

[0274] <Production Example of Toner External Additive Particles 10>

[0275] 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 raw material solution was added dropwise in the polycondensation step was changed to 1.0 hour. Table 1 shows the physical properties of the obtained toner external additive particles 10.

[0276] <Production Example of Toner External Additive Particles 11>

[0277] 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.

[0278] <Production Example of Toner External Additive Particles 12>

[0279] 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.

[0280] <Production Example of Toner External Additive Particles 13>

[0281] Toner External Additive Particles 13 were obtained in the same manner as in the 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.

[0282] <Production Example of Toner External Additive Particles 14>

[0283] Toner External Additive Particles 14 were obtained in the same manner as in the 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.

[0284] <Production Example of Toner External Additive Particles 15>

[0285] Toner External Additive Particles 15 were obtained in the same manner as in the 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.

[0286] <Production Example of Toner External Additive Particles 16>

[0287] 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.

[0288] <Production Example of Toner External Additive Particles 17>

[0289] 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.

[0290] <Production Example of Toner External Additive Particles 18>

[0291] Except that the amount of tetraethoxysilane was changed to 23.5 g and the amount of dimethyldimethoxysilane was changed to 30.9 g in the hydrolysis process, 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.

[0292] <Production Example of Toner External Additive Particles 19>

[0293] Except that the amount of tetraethoxysilane was changed to 33.8 g and the amount of dimethyldimethoxysilane was changed to 20.6 g in the hydrolysis process, toner external additive particles 19 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 19.

[0294] <Production Example of Toner External Additive Particles 20>

[0295] 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 raw material solution was added dropwise in the polycondensation step was changed to 2.5 hours. Table 1 shows the physical properties of the obtained toner external additive particles 20.

[0296] <Production Example of Toner External Additive Particles 21>

[0297] 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 raw material solution was added dropwise in the polycondensation step was changed to 1.0 hour. Table 1 shows the physical properties of the obtained Toner External Additive Particles 21.

[0298] <Production Example of Toner External Additive Particles 22>

[0299] Toner external additive particles 22 were obtained in the same manner as in the production example of toner external additive particles 1, except that 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 in the hydrolysis step. Table 1 shows the physical properties of the obtained toner external additive particles 22.

[0300] <Production Example of Toner External Additive Particles 23>

[0301] In the hydrolysis step, except that 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, the toner external additive particles 23 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 23.

[0302] <Production Example of Toner External Additive Particles 24>

[0303] Toner external additive particles 24 were obtained in the same manner as in the production example of toner external additive particles 1, except that tetraethoxysilane was not added in the hydrolysis step, 45.2 g of trimethoxymethylsilane and 9.2 g of dimethyldimethoxysilane were added instead, and 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.

[0304] <Production Example of Toner External Additive Particles 25>

[0305] Toner external additive particles 25 were obtained in the same manner as in the production example of toner external additive particles 18, except that the stirring temperature was set to 50° C. and the stirring time was set to 1.0 hour in the hydrolysis step, and the stirring time of the mixed solution after the raw material solution was added dropwise in the polycondensation step was changed to 1.0 hour. Table 1 shows the physical properties of the obtained toner external additive particles 25.

[0306] <Production Example of Toner External Additive Particles 26>

[0307] Toner external additive particles 26 were obtained in the same manner as in the production example of toner external additive particles 18, except that the amount of tetraethoxysilane was changed to 22.1 g, the amount of dimethyldimethoxysilane was changed to 32.3 g, the stirring temperature was set to 50° C., and the stirring time was set to 1.0 hour in the hydrolysis step, and the stirring time of the mixed solution after the raw material solution was added dropwise was changed to 1.0 hour in the polycondensation step. Table 1 shows the physical properties of the obtained toner external additive particles 26.

[0308] <Production Example of Toner External Additive Particles 27>

[0309] Toner external additive particles 27 were obtained in the same manner as in the production example of toner external additive particles 1, except that tetraethoxysilane and dimethyldimethoxysilane were not added in the hydrolysis step, 54.4 g of trimethoxymethylsilane was added instead, 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 27.

[0310] <Production Example of Toner External Additive Particles 28>

[0311] In the production example of the toner external additive particles 27, except that the amount of trimethoxymethylsilane was changed to 50.6 g and 3.8 g of tetraethoxysilane was added, the toner external additive particles 28 were obtained in the same manner as in the production example of the toner external additive particles 27. Table 1 shows the physical properties of the obtained toner external additive particles 28.

[0312] <Production Example of Toner External Additive Particles 29>

[0313] Toner External Additive Particles 29 were obtained in the same manner as in the Production Example of Toner External Additive Particles 1, except that 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 in the hydrolysis step. Table 1 shows the physical properties of the obtained Toner External Additive Particles 29.

[0314] <Production Example of Toner External Additive Particles 30>

[0315] Toner external additive particles 30 were obtained in the same manner as in the production example of toner external additive particles 1, except that 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 in the hydrolysis step. Table 1 shows the physical properties of the obtained toner external additive particles 30.

[0316] <Production Example of Toner External Additive Particles 31>

[0317] 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 while stirring. After the addition was completed, the mixture was further stirred for 0.5 h and hydrolyzed to obtain a dispersion of silicon polymer particles having siloxane bonds.

[0318] After adding 95.0 g of hexamethyldisilazane to the dispersion of silicon polymer particles having siloxane bonds obtained in the above process, the dispersion was heated to 50°C to 60°C and stirred at room temperature for 3.0 hours. The powder in the dispersion was then recovered by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain toner external additive particles 31. Table 1 shows the physical properties of the obtained toner external additive particles 31.

[0319] <Production Example of Toner External Additive Particles 32>

[0320] Toner external additive particles 32 were obtained in the same manner as in the production example of toner external additive particles 31 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 32.

[0321]

[0322] In the table, Si-O-Si% is the ratio of the peak area attributable to siloxane bonds to the total peak area attributable to silicon polymers. "DH" is the hydrophobicity. "PD" is the number average particle size of primary particles, and "AC" is the average circularity.

[0323] <Production Example of Polyester Resin A1>

[0324]

[0325] 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 its accessories was placed in a mantle-type resistance heater. Next, the interior of the flask was replaced with nitrogen, the temperature was gradually increased while stirring, and the reaction was carried out while stirring at 200°C for 4 hours (first reaction step). Thereafter, 1.2 parts (0.006 parts by mole) of trimellitic anhydride (TMA) was added, and the reaction was carried out at 180°C for 1 hour (second reaction step) to obtain polyester resin A1. The acid value of polyester resin A1 was 5 mg KOH / g.

[0326] <Production Example of Polyester Resin A2>

[0327] - Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts (0.155 parts by mole)

[0328] -24.1 parts (0.145 molar parts) of terephthalic acid

[0329] - 0.6 parts of tetrabutoxytitanium

[0330] 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 its accessories was placed in a mantle-type resistance heater. Next, the interior of the flask was replaced with nitrogen, the temperature was gradually increased while stirring, and the reaction was carried out while stirring at 200°C for 2 hours. Thereafter, 5.8 parts (0.030 parts by mole) of trimellitic anhydride was added, and the mixture was reacted at 180°C for 10 hours to obtain polyester resin A2. The acid value of polyester resin A2 was 10 mg KOH / g.

[0331] <Production Example of Polyester Resin A3>

[0332]

[0333] 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 its accessories was placed in a mantle-type resistance heater. Next, the interior of the flask was replaced with nitrogen, the temperature was gradually increased while stirring, and the reaction was carried out while stirring at 200°C for 2 hours. Thereafter, 8.2 parts (0.039 parts by mole) of trimellitic anhydride (TMA) was added, and the mixture was reacted at 160°C for 15 hours to obtain polyester resin A3. The acid value of polyester resin A3 was 20 mg KOH / g.

[0334] <Production Example of Polyester Resin A4>

[0335] - Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 parts by mole)

[0336] - 24.1 parts (0.140 parts by mole) of terephthalic acid (TPA)

[0337] - 0.5 parts of tetrabutoxytitanium

[0338] 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 its accessories was placed in a mantle-type resistance heater. Next, the interior of the flask was replaced with nitrogen, the temperature was gradually increased while stirring, and the reaction was carried out while stirring at 200°C for 4 hours. Thereafter, 5.3 parts (0.024 parts by mole) of trimellitic anhydride (TMA) was added, and the mixture was reacted at 180°C for 1 hour to obtain polyester resin A4. The acid value of polyester resin A4 was 25 mg KOH / g.

[0339] <Production Example of Toner Particles 1>

[0340]

[0341]

[0342] The raw materials in the above formulation were mixed using a Henschel mixer (FM-75 type, manufactured by Nippon Coke & Engineering Co., Ltd.) for 20 seconds. -1 The mixture was 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 at 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).

[0343] Furthermore, a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) was used for classification to obtain toner particles 1. Herein, the operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) involved rotating the machine at 50.0 s -1 The classification was performed at a classification rotor rotation speed of 100 Å. The weight average particle size (D4) of the obtained toner particles 1 was 5.9 μm.

[0344] <Production Example of Toner Particles 2>

[0345] Toner Particles 2 were obtained in the same manner as in the Production Example of Toner Particles 1, except that Polyester Resin A1 was changed to Polyester Resin A3. The weight average particle diameter (D4) of the obtained Toner Particles 2 was 5.9 μm.

[0346] <Production Example of Toner Particles 3>

[0347] Toner Particles 3 were obtained in the same manner as in the Production Example of Toner Particles 1, except that Polyester Resin A1 was changed to Polyester Resin A4. The weight average particle diameter (D4) of the obtained Toner Particles 3 was 5.9 μm.

[0348] <Production Example of Toner 1>

[0349] -Toner particles 1 100 parts

[0350] - 6.0 parts of external additive particles for toner

[0351] The above materials were mixed with a Henschel mixer FM-10C (manufactured by Mitsui Miike Machinery Co., Ltd.) for 30 seconds. -1 The mixture was mixed at a rotation speed of 0.05 and a rotation time of 10 min to obtain Toner 1.

[0352] <Production Examples of Toners 2 to 34>

[0353] Toners 2 to 34 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.

[0354] [Table 2]

[0355]

[0356] In the table, the addition amount is in parts relative to 100 parts of toner particles.

[0357] <Production Example of Carrier 1>

[0358] -Magnet 1 (magnetization intensity is 65Am under a magnetic field of 1000 / 4π(kA / m) 2 / kg), and the number average particle size was 0.30 μm.

[0359] -Magnet 2 (magnetization intensity is 65Am under a magnetic field of 1000 / 4π(kA / m) 2 / kg), and the number average particle size was 0.50 μm.

[0360] Here, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added to 100 parts of each material or more, mixed and stirred at high speed at 100° C. or more in a container to treat each fine particle.

[0361] - Phenol: 10% by mass

[0362] -Formaldehyde solution: 6% by mass (40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water)

[0363] - Magnet 1 treated with the above silane compound: 58% by mass

[0364] - Magnet 2 treated with the above silane compound: 26% by mass

[0365] Then, 100 parts of the above materials, 5 parts of 28% by mass ammonia solution and 20 parts of water were put into a flask, and the temperature was raised to 85°C over 30 minutes while mixing by stirring, and the polymerization reaction was carried out for 3 hours by maintaining the temperature to solidify the generated phenolic resin. The solidified phenolic resin was then cooled to 30°C, and then further water was added, after which the supernatant was removed and the precipitate was washed with water and subsequently air-dried. Next, the resulting product was dried under reduced pressure (5 mmHg or less) at a temperature of 60°C 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.

[0366] <Production Example of Two-Component Developer 1>

[0367] Here, 8.0 parts of Toner 1 is added to 92.0 parts of Carrier 1 and mixed using a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain Two-Component Developer 1 .

[0368] <Production Examples of Two-Component Developers 2 to 34>

[0369] Two-component developers 2 to 34 were produced in the same manner as in the production example of the two-component developer 1, except that the toners were changed as shown in Table 3 here.

[0370] [Table 3]

[0371] 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

[0372] <Toner Evaluation Method>

[0373] (1) Measurement of image density changes

[0374] A Canon full-color copier, imagePress C800, was used as an image forming apparatus. A two-component developer was placed in a cyan developing device of the image forming apparatus, and a toner was placed in a cyan toner container for the following evaluation. The apparatus was modified by disassembling 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.).

[0375] 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 expressing 256 gray levels in hexadecimal, 00h is the 1st gray level (white background portion) of the 256 gray levels, and FF is the 256th gray level (solid portion) of the 256 gray levels. First, an image output test of 1000 images was performed at an image ratio of 1%. During the continuous passage of 1000 sheets, the paper was passed under the same development conditions and transfer conditions as the first sheet (uncalibrated).

[0376] After this, 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 paper was passed under the same development and transfer conditions as the first sheet (uncalibrated). The density of the 1,000th sheet when printed at an image ratio of 1% was taken as the initial density, and the density of the 1,000th sheet when printed at an image ratio of 80% was measured and evaluated.

[0377] The above test was conducted under a normal temperature and normal humidity environment (N / N; temperature 25°C, relative humidity 55%), under a high temperature and high humidity environment (H / H; temperature 30°C, relative humidity 80%), and under a normal temperature and low humidity environment (N / L; temperature 23°C, relative humidity 5%). Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite, Inc.), the initial density and the density of the 1000th image when printed at an image ratio of 80% were measured, and the difference Δ thereof was used to perform rating according to the following criteria.

[0378] (Evaluation criteria: image density difference Δ)

[0379] A: less than 0.02

[0380] B: 0.02 or more and less than 0.05

[0381] C: 0.05 or more and less than 0.10

[0382] D: 0.10 or more and less than 0.15

[0383] E: 0.15 or more

[0384] (2) Method for evaluating fogging on non-image areas (white background areas) after durability

[0385] A modified full-color copier manufactured by Canon, Image RUNNER ADVANCE C5255, was used, and two-component developer 1 was placed in the developing device of the cyan station for evaluation. The toner load on paper in the FFh image (solid image) was adjusted to 0.45 mg / cm 2 The evaluation environment was N / N, H / H and N / L environment, and the evaluation paper was plain copy paper GFC-081 (A4, basis weight 81.4 g / m 2 , sold by Canon Marketing Japan Inc.). In each environment, a FFh image of 1 cm×1 cm was output at the center of an A4 paper, and fogging on a white background was measured after outputting 50,000 sheets.

[0386] The reflectivity Dr (%) of the evaluation paper before imaging was measured using a reflectometer ("REFLECTOMETER MODEL TC-6DS" manufactured by Tokyo Denshoku Co., Ltd.). After aging (sheet 50001), the reflectivity Ds (%) of the 00H image area (white background area) was measured. From the obtained Dr and Ds, fogging (%) was calculated using the following formula.

[0387] Fogging (%) = Dr (%) - Ds (%)

[0388] The evaluation results were rated according to the following criteria.

[0389] (Evaluation criteria: Fogging (%))

[0390] A: less than 1.0%

[0391] B: 1.0% or more and less than 1.5%

[0392] C: 1.5% or more and less than 2.0%

[0393] D: 2.0% or more and less than 2.5%

[0394] E: 2.5% or more

[0395] (3) Methods for evaluating charging stability

[0396] The triboelectric charge of the toner is calculated by attracting and capturing 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, with the inner cylinder insulated from the outer cylinder. When a charged body with a charge of Q is placed in the inner cylinder, due to electrostatic induction, it is as if a metal cylinder with a charge of Q exists. This induced charge is measured using 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.

[0397] Triboelectric charge of toner (mC / kg) = Q / M

[0398] Evaluation image: Place a 2cm x 5cm FFh ​​image in the center of an A4 paper

[0399] 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 captured using a cylindrical tube and a cylindrical filter, and the initial Q / M ratio was measured. Subsequently, the evaluation machine, equipped with a developing device, was placed in N / N, H / H, and N / L environments for two weeks. The same procedures as before the placement were then performed, and the charge per unit mass Q / M (mC / kg) on ​​the latent electrostatic image bearing member after the placement was measured. The rate of change in Q / M after placement ([initial Q / M] - [Q / M after placement in each environment]) × 100 / [initial Q / M] was calculated from the initial Q / M per unit mass on the latent electrostatic image bearing member and the Q / M per unit mass on the latent electrostatic image bearing member after the placement, and evaluated according to the following criteria.

[0400] (Evaluation Criteria)

[0401] A: The change rate is less than 2%

[0402] B: Change rate is 2% or more and less than 5%

[0403] C: Change rate is 5% or more and less than 10%

[0404] D: The change rate is 10% or more and less than 15%

[0405] E: Change rate is more than 15%

[0406] <Evaluation Results of Examples 1 to 27>

[0407] Table 4 shows the evaluation results of Examples 1 to 27.

[0408] <Evaluation Results of Comparative Examples 1 to 7>

[0409] Table 4 shows the evaluation results of Comparative Examples 1 to 7.

[0410]

[0411] In the table, “CE” stands for “Comparative Example”, “FV” stands for “Fog Value”, and “CR” stands for “Rate of Change”.

[0412] <Production Examples of Toners 35 to 39>

[0413] Toners 35 to 39 were obtained by production 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 5.

[0414] [Table 5]

[0415]

[0416] <Production Examples of Two-Component Developers 35 to 39>

[0417] Two-component developers 35 to 39 were obtained by producing in the same manner as in the production example of the two-component developer 1 except that the toner was changed as shown in Table 6.

[0418] [Table 6]

[0419] Two-component developer No. Toner No. Carrier No. 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 Two-component developer 39 Toner 39 Carrier 1

[0420] <Evaluation Results of Examples 28 to 32>

[0421] Table 7 shows the evaluation results of Examples 28 to 32.

[0422]

[0423] In the table, “FV” means “Fog Value”, and “CR” means “Change Rate”.

[0424] 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. A toner external additive comprising a siloxane bond and a Si-R 1 Bonded silicon polymer particles, characterized in that The R 1 represents an alkyl group having 1 to 6 carbon atoms, By the external additive 29 In the graph obtained by Si-NMR measurement, the total peak area attributable to the external additive is represented by A, and the total peak area attributable to the Si-R 1 In the case where the peak area of ​​the bond is represented by B, the A and the B satisfy the following formula (1), and By the external additive 29 In the graph obtained by Si-NMR measurement, when the total peak area attributed to the silicon polymer is represented by SA and the peak area attributed to the T unit structure is represented by S3, the SA and S3 satisfy the following formula (2), 0.260≤B / A≤0.450 ...(1) 0.00≤S3 / SA≤0.50 ...(2).

2. The external additive for toner according to claim 1, wherein The silicon polymer has the siloxane bond, the Si-R 1 bond, and Si-OR 2 key, and By the external additive 29 In the graph obtained by Si-NMR measurement, in the graph attributable to the Si-OR contained in the external additive, 2 When the peak area is represented by C, the following formula (3) is satisfied: 0.050≤(C / A) / (B / A)≤0.180 ...(3) wherein R 2 represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. 3 . 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. 4 . The toner external additive according to claim 1 , wherein 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 oils. 5 . The external additive for toner according to claim 1 , wherein the external additive has an average circularity of 0.85 to 0.

95.

6. The external additive for toner according to claim 1 or 2, wherein the 29 The ratio of the peak area attributable to the siloxane bond in the total peak area attributable to the silicon polymer calculated from a chart obtained by Si-NMR measurement is 60.0% to 85.0%.

7. The external additive for toner according to claim 1 or 2, wherein 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 following formulae (I) to (III) are satisfied, 0.20≤S4 / SA≤0.60 ...(I) 0.00≤S3 / SA≤0.50 ...(II) 0.20≤S2 / SA≤0.70...(III). 8 . 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. 9 . The external additive for toner according to claim 1 , wherein the hydrophobicity of the external additive measured by methanol titration is 50% to 60%.

10. A toner comprising toner particles and an external additive for a toner, characterized in that: The toner particles contain a binder resin, and The external additive for toner is the external additive for toner according to claim 1 or 2.

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