Fine particles, toner additives, and toner

Abstract

To provide a fine particle that has durable stability and charge stability in a high temperature and high humidity environment, and can prevent a variation in density regardless of an image printing ratio.SOLUTION: Fine particles of a silicon polymer are provided. The fine particle has pores. The total volume of the pores in the fine particle is 0.35 cm3 / g to 1.00 cm3 / g. The number average particle diameter of primary particles of the fine particles is 0.05 μm to 0.30 μm. The silicon polymer has a siloxane bond and a Si-R1 bond. The R1 represents an alkyl group having 1 to 6 carbon atoms. In a chart obtained in 29Si-NMR measurement of the fine particles, when the total peak area corresponding to the silicon polymer is defined as A, and the peak area corresponding to the Si-R1 is defined as B, the A and the B satisfy the following formula (1). (1) 10.0≤B / A×100≤45.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to fine particles, toner additives, and toner used in electrophotographic systems using said toner additives. [Background technology]

[0002] In recent years, with the widespread adoption of electrophotographic full-color copiers, there has been an increasing demand for toners used in electrophotography to support high-speed printing, improve environmental stability, and extend lifespan. Traditionally, silica has been widely known as an external additive used in toners. Generally, examples have been reported of silica obtained by dry or wet (sol-gel) processes being surface-treated to enhance its hydrophobicity.

[0003] For example, Patent Document 1 describes an example in which highly hydrophobic spherical sol-gel silica fine particles were added to toner matrix particles to improve the electrostatic stability of the toner. Furthermore, as described in Patent Document 2, there is an example in which the amount of silanol groups and pore volume of silica were specified to improve the environmental stability and electrostatic stability of the toner. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2007-099582 [Patent Document 2] Japanese Patent Publication No. 2016-080886 [Patent Document 3] International Publication No. 2015 / 107961 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, when printing images in a high-temperature, high-humidity environment over a long period, the silica present on the toner surface becomes more susceptible to the effects of moisture inside the image output device, which can cause changes in the toner surface condition. This can alter the toner's charge properties, resulting in variations in image density. Furthermore, under conditions that place significant stress on the toner, such as printing a large volume of low-resolution images, color fluctuations in the images may occur, indicating that there is still room for improvement in terms of toner's charge stability and durability.

[0006] On the other hand, Patent Document 3 describes an example in which polyalkylsilsesquioxane fine particles were added to toner matrix particles to improve the fluidity and electrostatic stability of the toner. However, in all of these technologies, when outputting images in high-temperature and high-humidity environments, or when outputting large quantities of low-print images, there are challenges with the hygroscopicity and durability stability of the external additives, and it was found that there is room for improvement in terms of image density stability and environmental stability.

[0007] This disclosure provides fine particles, an external additive for toner, and a toner using the external additive, which have durable stability and electrostatic stability in high temperature and high humidity environments, and which can suppress density fluctuations regardless of the image printing ratio. [Means for solving the problem]

[0008] This disclosure relates to silicon polymer nanoparticles, The fine particles have pores, The total pore volume of the fine particles is 0.35 cm³. 3 / g~1.00cm 3 / g The number-average particle size of the primary particles of the fine particles is 0.05 μm to 0.30 μm. The silicon polymer has siloxane bonds and Si-R 1 Having a bond, Applicable R 1 This represents an alkyl group with 1 to 6 carbon atoms. The fine particles 29In the chart obtained by Si-NMR measurement, the total peak area corresponding to the silicon polymer is denoted as A, and the Si-R 1 When the corresponding peak area is B, A and B are given by the following formula (1) 10.0 ≤ B / A × 100 ≤ 45.0 ···(1) Regarding fine particles that satisfy the following conditions. [Effects of the Invention]

[0009] This disclosure provides fine particles, an external additive for toner, and a toner using the external additive, which have durable stability and electrostatic stability in high temperature and high humidity environments, and which can suppress density fluctuations regardless of the image printing ratio. [Modes for carrying out the invention]

[0010] In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be combined in any way.

[0011] The inventors believe the mechanism by which the above effects occur is as follows: Conventionally, typical sol-gel silica particles used as external additives for toner are particles mainly composed of siloxane bonds (Si-O-Si). Normally, silanol groups are present at the ends of sol-gel silica particles, and therefore unreacted residual silanol groups exist on the surface and inside the silica particles. These residual silanol groups combine with water molecules in the air, causing the toner's chargeability to decrease when used in high-temperature and high-humidity environments for extended periods. In addition, moisture can enter through the pores in the silica particles and is difficult to release, which also causes a decrease in the toner's chargeability. Thus, when sol-gel silica particles are used in high-temperature and high-humidity environments, the chargeability of the toner tends to decrease.

[0012] As a result of diligent research by the inventors, the pore volume of the fine particles and the Si-R inside the fine particles were found to be related. 1 (R1 It has been found that the above problem can be solved by optimizing the abundance of (which is an alkyl group having 1 to 6 carbon atoms). Regarding the mechanism, it is considered that by introducing an alkyl group such as SiCH3 into the fine particles, it becomes difficult for moisture to enter the pores of the fine particles, and the hydrophobicity is enhanced. It is also presumed that by having an appropriate pore volume, external stress is alleviated and the surface charge is stabilized, so that changes in the charge amount of toner under high temperature and high humidity environments and changes in the surface state of toner caused by low print image output can be suppressed. Furthermore, it is presumed that by having an appropriate pore volume, external stress is alleviated and changes in toner charge amount can be suppressed, so that durability stability is improved and fogging after durable use can be suppressed.

[0013] The present disclosure relates to fine particles of a silicon polymer, the fine particles have pores, the total pore volume of the fine particles is 0.35 cm 3 / g to 1.00 cm 3 / g, the number average particle diameter of primary particles of the fine particles is 0.05 μm to 0.30 μm, the silicon polymer has a siloxane bond and Si-R 1 bond, the R 1 represents an alkyl group having 1 to 6 carbon atoms, of the fine particles 29 in a chart obtained by Si-NMR measurement, when the total peak area corresponding to the silicon polymer is defined as A, and the peak area corresponding to the Si-R 1 is defined as B, the A and the B satisfy the following formula (1) 10.0≦B / A×100≦45.0 ···(1) relates to fine particles satisfying the above.

[0014] The fine particles have pores, and the total pore volume of the fine particles is 0.35 cm 3 / g to 1.00 cm 3 / g. Specifically, this refers to the total pore volume of the fine particles measured by the BJH method in a pore diameter range of 1.7 nm or more and 300.0 nm or less.

[0015] The total pore volume of the microparticles is 0.35 cm³. 3 When the amount is less than / g, the fine particles cannot relieve the stress and strain they receive from materials, etc. As a result, the fine particles become embedded in the surface of the toner particles, and the adhesion force of the toner changes, making it impossible to suppress color variations in the image caused by fluctuations in the amount of toner applied to the paper.

[0016] The total pore volume of the fine particles is 1.00 cm³. 3 When the value is greater than / g, the ratio of pore volume to the total volume of the fine particles becomes too high, resulting in insufficient mechanical strength of the fine particles. This causes the fine particles themselves to collapse due to stress and pressure from materials, etc. As a result, the adhesion force of the toner changes, making it impossible to suppress color variations in the image caused by fluctuations in the amount of toner applied to the paper.

[0017] The total pore volume of the fine particles is preferably 0.35 cm³. 3 / g or more 0.80cm 3 It is less than or equal to / g, and more preferably 0.40cm 3 / g or more 0.60cm 3 It is less than or equal to / g, and more preferably 0.41cm 3 / g or more 0.50cm 3 It is less than / g. In the wet manufacturing method, the total pore volume of the fine particles can be controlled by the hydrolysis and condensation conditions during the reaction (reaction temperature, reaction time, stirring time), the pH during the reaction, the type of catalyst, and the ratio of added monomers.

[0018] For example, to increase the total pore volume, methods include increasing the mixing ratio of bifunctional silanes, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the pH of the solution, and lowering the temperature during hydrolysis. In particular, the temperature during the condensation reaction affects pore formation, and by controlling the temperature range during the condensation reaction to 15-25°C, the formation of siloxane bonds is suppressed, making it easier to keep the total pore volume of the fine particles within the specified range. To decrease the total pore volume, methods include increasing the mixing ratio of tetrafunctional silanes, raising the temperature during the condensation reaction, lengthening the stirring time, raising the pH of the solution, and raising the temperature during hydrolysis.

[0019] Silicon polymers have siloxane bonds and Si-R 1 (R) 1 (This represents an alkyl group with 1 to 6 carbon atoms). And the fine particles 29 In the chart obtained by Si-NMR measurement, the total peak area corresponding to the silicon polymer is denoted as A, and Si-R 1 When the corresponding peak area is denoted as B, then A and B satisfy the following equation (1). 10.0 ≤ B / A × 100 ≤ 45.0 ···(1)

[0020] 29 In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional group bonded to Si in the constituent compounds of silicon polymers. By identifying each peak position using a standard sample, the structure bonded to Si can be determined. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak areas. The ratio of the peak areas 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 calculated.

[0021] [ka]

[0022] Ra, Rb, Rc, Rd, Re, and Rf each independently represent an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2, and even more preferably 1). Furthermore, of the total peak area A, Si-R 1 The ratio of peak area B corresponding to the bond (B / A) is the Si-R contained in the nanoparticles. 1 This is the relative abundance of Si-R. 1 This indicates that at least one alkyl group having 1 to 6 carbon atoms is bonded to Si. For example, this is the sum of the portions in S1, S2, and S3 where Si is bonded to alkyl groups having 1 to 6 carbon atoms. By satisfying formula (1), the amount of alkyl groups present near the pores in the fine particles is optimized, improving the environmental stability and electrostatic stability of the toner. 10.0 ≤ B / A × 100 ≤ 45.0 ···(1) Si-R 1 In R 1 represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2, and even more preferably 1).

[0023] If B / A × 100 is less than 10.0, the amount of alkyl groups near the pores within the microparticles is too low, making it easier for moisture to be absorbed into the pores, and thus the effect of electrostatic stability in high-temperature, high-humidity environments is not achieved. Also, if B / A × 100 exceeds 45.0, the amount of siloxane bonds near the pores within the microparticles becomes relatively low, making them more susceptible to fracture or collapse when subjected to external stress, with the pores acting as the starting point. In other words, the durability of the microparticles themselves is reduced.

[0024] Preferably, 20.0 ≤ B / A × 100 ≤ 45.0, more preferably 25.0 ≤ B / A × 100 ≤ 40.0, and even more preferably 25.0 ≤ B / A × 100 ≤ 35.0. Within this range, the durability stability of the toner and the electrostatic stability in high temperature and high humidity environments are further improved from the above viewpoint.

[0025] The method for producing silicon polymer fine particles is not particularly limited, but it is preferable to form particles by hydrolysis and condensation polymerization of a silicon compound (silane monomer) by the sol-gel method. Specifically, a mixture of a bifunctional silane having two siloxane bonds and a tetrafunctional silane having four siloxane bonds is polymerized by hydrolysis and condensation polymerization. It is preferable to form particles in this way. Silane monomers such as bifunctional silanes and tetrafunctional silanes will be described later.

[0026] In other words, the silicon polymer is preferably a condensate polymer of at least one silicon compound selected from the group consisting of difunctional silanes and at least one silicon compound selected from the group consisting of tetrafunctional silanes. The proportion of difunctional silane is preferably 50 mol% to 75 mol%, more preferably 55 mol% to 70 mol%. The proportion of tetrafunctional silane is preferably 25 mol% to 50 mol%, more preferably 30 mol% to 45 mol%.

[0027] The inventors have found that the above-mentioned effects can be achieved in a method for producing fine particles by adjusting the mixing ratio of the monomers, the solvent temperature during hydrolysis and condensation reactions, the type of catalyst, the stirring time, and the pH of the solution.

[0028] For example, to increase the B / A ratio, methods include increasing the mixing ratio of the bifunctional silane, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the pH of the solution, and lowering the temperature during hydrolysis. To decrease the B / A ratio, methods include increasing the mixing ratio of the tetrafunctional silane, raising the temperature during the condensation reaction, lengthening the stirring time, raising the pH of the solution, and raising the temperature during hydrolysis.

[0029] The fine particles of this disclosure have particles of a silicon polymer having siloxane bonds. The silicon polymer particles preferably contain 90% by mass or more, more preferably 95% by mass or more of the silicon polymer.

[0030] The method for producing silicon polymer particles is not particularly limited. For example, a silane compound can be added dropwise to water, hydrolyzed and condensed using a catalyst, and the resulting suspension can be filtered and dried. The particle size can be controlled by the type of catalyst, the mixing ratio, the reaction initiation temperature, and the dropping time. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide, but the method is not limited to these.

[0031] Silicon polymer particles are preferably produced by the following method. Specifically, the method preferably includes a first step of obtaining a hydrolysate of a silicon compound, a second step of mixing the hydrolysate with an alkaline aqueous medium to cause a polycondensation reaction of the hydrolysate, and a third step of mixing the polycondensation reaction product with an aqueous solution to form particles. In some cases, a hydrophobic agent may be further added to the spherical silicon polymer particle dispersion to obtain hydrophobic spherical silicon polymer particles.

[0032] The first step involves contacting a silicon compound and a catalyst in an aqueous solution prepared by stirring, mixing, or other means. Any known catalyst can be suitably used as the catalyst. Specifically, examples of acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0033] The amount of catalyst used can be appropriately adjusted depending on the type of silicon compound and catalyst. Preferably, 1 × 10⁶ of catalyst is used per 100 parts by mass of water used when hydrolyzing the silicon compound. -3 Selected within the range of ~1 part by mass.

[0034] Catalyst usage amount 1 × 10 -3 If the amount of catalyst is greater than or equal to parts by mass, the reaction will proceed sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles will be low, making hydrolysis easier. The amount of water used is preferably 2 to 15 moles per mole of silicon compound. The hydrolysis reaction proceeds sufficiently when the amount of water is 2 moles or more, and productivity improves when it is 15 moles or less.

[0035] The reaction temperature is not particularly limited and may be carried out at room temperature or under heating conditions. However, it is preferable to carry out the reaction at a temperature of 10 to 60°C, as this allows for the acquisition of hydrolysates in a short time and suppresses the partial condensation reaction of the resulting hydrolysates. The reaction time is not particularly limited and should be appropriately selected considering the reactivity of the silicon compound used, the composition of the reaction solution prepared by combining the silicon compound, acid, and water, and the productivity.

[0036] 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 cause a polycondensation reaction of the particle precursor. This yields a polycondensation reaction solution. Here, the alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0037] The alkaline components used in alkaline aqueous media are those whose aqueous solutions exhibit basic properties, acting as a neutralizing agent 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.

[0038] The amount of alkaline component used is such that it neutralizes the acid and acts effectively as a catalyst for the polycondensation reaction. For example, when ammonia is used as the alkaline component, it is usually selected in the range of 0.01% to 12.5% ​​by mass per 100 parts by mass of the mixture of water and organic solvent.

[0039] In the second step, an organic solvent may be used in addition to the alkaline component and water to prepare an alkaline aqueous medium. The organic solvent is not particularly limited as long as it is miscible with water, but an organic solvent that dissolves 10 g or more of water per 100 g at room temperature and atmospheric pressure is preferred.

[0040] Specifically, examples include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethers such as ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0041] Among the organic solvents listed above, alcohol-based solvents such as methanol, ethanol, 2-propanol, and butanol are preferred. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reactions, it is even more preferable to select the same alcohol as the alcohol produced by elimination as the organic solvent.

[0042] In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution and atomized. Water (tap water, pure water, etc.) can be suitably used as the aqueous solution, but components that are compatible with water, such as salts, acids, alkalis, organic solvents, surfactants, and water-soluble polymers, may be further added to the water. The temperature of the polycondensation reaction solution and the aqueous solution during mixing is not particularly limited, but a range of 5 to 70°C is suitably selected considering their composition, productivity, etc.

[0043] Methods for recovering silicon polymer particles can be any known method without particular limitations. For example, the suspended powder can be scooped up, or a filtration method may be employed, but filtration is preferred because it is easy to operate. The filtration method is not particularly limited and can be vacuum filtration or centrifugal filtration. You can choose any known device, such as pressurized filtration. The filter paper, filters, and filter cloth used for filtration are not particularly limited as long as they are industrially available, and can be appropriately selected according to the device used.

[0044] The silicon polymer particles may be surface-treated using known methods such as silane coupling agents or silicone oils to adjust their degree of hydrophobicity.

[0045] The monomer used can be appropriately selected depending on its compatibility with the solvent and catalyst, or its hydrolyzability, but tetraethoxysilane is preferred as the tetrafunctional silane. Dimethyldimethoxysilane is preferred as the bifunctional silane.

[0046] The silicon polymer is preferably a condensed polymer of at least one silicon compound selected from the group consisting of silicon compounds having a structure represented by the following formula (A). [ka]

[0047] In formula (A), R 12 , R 13 , R 14 and R 15 Each independently represents an alkyl group, phenyl group, or reactive group (for example, a halogen atom, a hydroxyl group, an acetoxy group, or an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably 1 or 2 carbon atoms)) having 1 to 6 carbon atoms. 12 , R 13 , R 14 and R 15 At least one of them is the reaction group. R 12 , R 13 , R 14 and R 15 Each of these is preferably an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2 carbon atoms), or an alkoxy group (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms).

[0048] To obtain silicon polymer particles, a silicon compound having four reactive groups in one molecule of formula (A) (tetrafunctional silane), and R in formula (A) 12The group is an alkyl group or a phenyl group, and there are three reactive groups (R 13 , R 14 , R 15 ) an organosilicon compound (trifunctional silane), R in formula (A) 12 , R 13 The alkyl group is an alkyl group or a phenyl group, and the two reactive groups (R 14 , R 15 ) an organosilicon compound (difunctional silane), R in formula (A) 12 , R 13 , R 14 is an alkyl group or a phenyl group, and one reactive group (R 15 ) organosilicon compounds (monofunctional silanes) having ) can be used. Note that in the above silicon compounds, if R is not a reactive group, 12 ~R 14 Preferably, it is an alkyl group having 1 to 6 carbon atoms.

[0049] These reactive groups undergo hydrolysis, addition polymerization, and condensation polymerization to form a crosslinked structure, thereby obtaining silicon polymer particles. 13 , R 14 and R 15 Hydrolysis, addition polymerization, and condensation polymerization can be controlled by the reaction temperature, reaction time, reaction solvent, and pH.

[0050] Examples of tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanatesilane.

[0051] Examples of trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, and Tyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethyltrimethoxysilane, Examples include butyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0052] Examples of bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and diethyldimethoxysilane. Examples include orchids.

[0053] Examples of monofunctional silanes include t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, and triphenylethoxysilane.

[0054] The volume-average diameter of the pores in the fine particles is preferably between 7 nm and 20 nm. When the volume-average diameter of the pores is within this range, moisture is less likely to penetrate the fine particles, resulting in excellent electrostatic stability in high-temperature and high-humidity environments. Furthermore, the mechanical strength of the fine particles is appropriately maintained, resulting in excellent durability and stability, and further suppression of color variations in images caused by fluctuations in the amount of toner applied to the paper.

[0055] When the average diameter of the pores is 7 nm or more, it is easier to mitigate external forces from materials and other sources. Therefore, it is easier to obtain a greater effect on durability and stability, and it is also possible to further suppress color variations in images caused by fluctuations in the amount of toner applied on the paper. When the average diameter of the pores is 20 nm or less, it is easier to obtain a greater effect on suppressing the penetration of moisture into the fine particles, and the robustness of the fine particles is improved, making them less prone to crushing or breakage. From the above viewpoint, the volume average diameter of the pores is preferably 10 nm to 18 nm, and more preferably 11 nm to 16 nm. The volume-average diameter of the pores can be increased by reducing the proportion of methanol and increasing the amount of catalyst. Conversely, the volume-average diameter of the pores can be decreased in the condensation polymerization process by increasing the proportion of methanol and decreasing the amount of catalyst.

[0056] The theoretical BET specific surface area of ​​a fine particle is X(m²). 2 The measurement was performed using the BET multipoint method for fine particles ( / g). The specific surface area of ​​the BET is Y(m 2 When / g), it is preferable that X and Y satisfy the following formula (2). 3.0 ≤ Y / X ≤ 8.0 ···(2)

[0057] Since fine particles satisfying equation (2) are highly porous, their durability and stability against stress and external forces from components can be effectively improved. When Y / X is 3.0 or greater, the number of pores or the pore volume within the fine particles is large, making it easier to obtain the effect of durability and stability. When Y / X is 8.0 or less, the number of pores or the pore volume within the fine particles is within a suitable range, improving the robustness of the fine particles and further suppressing crushing and breakage. From the above viewpoint, it is more preferable for Y / X to be 4.0 ≤ Y / X ≤ 6.0.

[0058] The Y / X ratio can be increased by lowering the reaction temperature and reducing the amount of catalyst in the polymerization condensation process. Conversely, the Y / X ratio can be decreased by raising the reaction temperature, lengthening the reaction time, and increasing the amount of catalyst in the polymerization condensation process. Y is preferably 75-300m 2 It is / g, more preferably 120~250m 2 / g, and more preferably 150-200m 2 / g. X is preferably 20-60m 2 / g, more preferably 25~50m 2 / g, and more preferably 30-40m 2 It is / g.

[0059] The number-average particle size of the primary particles of the fine particles must be between 0.05 μm and 0.30 μm. When the number-average particle size of the primary particles is within this range, it becomes easier to uniformly coat the toner particles with the fine particles. In addition, stress on the toner can be suppressed, making it easier to obtain the effect of static charge stability.

[0060] When the number-average particle size of the primary particles of the fine particles is less than 0.05 μm, the stress on the toner increases when printing a large amount of low-density images for a long period of time under harsh conditions such as high temperature and high humidity, making it easier for the external additive particles to become embedded in the toner surface. As a result, color variations in the image due to fluctuations in the amount of toner adhering to the paper cannot be suppressed, fogging is more likely to occur after extended use, and the electrostatic stability also decreases. Furthermore, when the number-average particle size of the primary particles of the fine particles exceeds 0.30 μm, the fine particles are more likely to detach from the toner surface. As a result, color variations in the image due to fluctuations in the amount of toner adhering to the paper cannot be suppressed, fogging is more likely to occur after extended use, and the electrostatic stability also decreases.

[0061] The number-average particle size of the primary particles of the fine particles is preferably 0.07 μm to 0.25 μm, more preferably 0.08 μm to 0.18 μm, and even more preferably 0.08 μm to 0.15 μm. The number-average particle size of the primary particles of the fine particles can be increased in the hydrolysis step by lowering the reaction temperature, shortening the reaction time, or increasing the amount of catalyst. Conversely, the number-average particle size of the primary particles of the fine particles can be decreased in the hydrolysis step by raising the reaction temperature, lengthening the reaction time, or decreasing the amount of catalyst.

[0062] In X-ray photoelectron spectroscopy measurements of the surface of fine particles, the elemental concentration of silicon is denoted as dSi, the elemental concentration of oxygen as dO, and the elemental concentration of carbon as dC, with a total of 100.0 atomic%. In this case, it is preferable that dC is between 10.0 atomic% and 50.0 atomic%, more preferably between 20.0 atomic% and 45.0 atomic%, and even more preferably between 25.0 atomic% and 40.0 atomic%. When dC is within the above range, it is preferable from the viewpoint of charge stability and durability stability in high temperature and high humidity environments.

[0063] When dC is 10.0 atomic% or higher, the amount of alkyl on the surface of the fine particles is sufficient, and the electrostatic stability in high temperature and high humidity environments is further improved. When the amount is below %, the alkyl content on the surface of the fine particles is appropriate, which improves the effect of suppressing external stress and results in better durability and stability.

[0064] The Young's modulus of the fine particles is preferably between 1500 MPa and 30000 MPa. When the Young's modulus is within this range, it can relieve stress when the toner is subjected to stress from components such as carriers, and further suppress the embedding of external additive particles into the surface of the toner particles.

[0065] When the Young's modulus is 1500 MPa or higher, the fine particles themselves are less likely to break down when the toner is subjected to stress from components such as carriers. Furthermore, when the Young's modulus is 30000 MPa or lower, the stress is more easily relieved when the toner is subjected to stress from components such as carriers, and the embedding of fine particles into the toner particle surface is further suppressed. As a result, the toner surface state is less likely to change, and changes in the toner's charge can be further suppressed.

[0066] The Young's modulus of the fine particles is more preferably 3000 MPa to 9000 MPa, and even more preferably 5000 MPa to 7000 MPa. The Young's modulus of the fine particles can be controlled by changing the mixing ratio of the above monomers, the hydrolysis and condensation conditions, the pH, and the type of catalyst.

[0067] The fine particles are preferably surface-treated with a hydrophobic agent. That is, the fine particles are preferably particles of a silicon polymer surface-treated with a hydrophobic agent. The hydrophobic agent is not particularly limited, but it is preferably an organosilicon compound.

[0068] Examples include alkylsilazane compounds such as hexamethyldisilazane, alkylalkoxysilane compounds such as diethyldiethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, and dodecyltrimethoxysilane, fluoroalkylsilane compounds such as trifluoropropyltrimethoxysilane, chlorosilane compounds such as dimethyldichlorosilane and trimethylchlorosilane, siloxane compounds such as octamethylcyclotetrasiloxane, or silicone oils and silicone varnishes.

[0069] Hydrophobic treatment of the surface of the fine particles can further suppress changes in the charge amount of toner in high-temperature and high-humidity environments. Among these, it is preferable that the fine particles are surface-treated with at least one compound selected from the group consisting of alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, fluoroalkylsilane compounds, siloxane compounds, and silicone oils. Furthermore, surface treatment of the fine particles with alkylsilazane compounds is more preferable from the viewpoint of charge stability in high-temperature and high-humidity environments.

[0070] The degree of hydrophobicity of fine particles obtained by methanol titration is preferably 30% to 65% by volume, more preferably 50% to 60% by volume, and even more preferably 53% to 58% by volume, from the viewpoint of electrostatic stability in high-temperature and high-humidity environments.

[0071] fine particles 29 In the chart obtained by Si-NMR measurement, when the total peak area corresponding to the silicon polymer is denoted as SA, the peak area corresponding to the Q unit structure as S4, the peak area corresponding to the T unit structure as S3, and the peak area corresponding to the D unit structure as S2, it is preferable that SA, S4, S3, and S2 satisfy the following formulas (I) to (III). 0.20 ≤ S4 / SA ≤ 0.60 ···(I) 0 ≤ S3 / SA ≤ 0.50 ···(II) 0.20≦S2 / SA≦0.70 (III)

[0072] Within the above range, when the toner is subjected to stress from components such as carriers, the embedding of fine particles into the toner particle surface and the destruction of the fine particles themselves can be further suppressed. Furthermore, it is more preferable that 0.30 ≤ S4 / SA ≤ 0.50, and even more preferable that 0.34 ≤ S4 / SA ≤ 0.40. Furthermore, it is more preferable that 0 ≤ S3 / SA ≤ 0.40, even more preferable that 0 ≤ S3 / SA ≤ 0.20, even more preferable that 0 ≤ S3 / SA ≤ 0.10, and particularly preferable that 0 ≤ S3 / SA ≤ 0.05. Furthermore, it is more preferable that 0.50 ≤ S2 / SA ≤ 0.70, and even more preferable that 0.60 ≤ S2 / SA ≤ 0.66. Within the above range, the Si-R of the fine particles 1 The optimal amount of [the substance] is preferable in terms of the environmental stability, electrostatic stability, and durability stability of the toner.

[0073] The average circularity of the fine particles is preferably 0.85 to 0.95 from the viewpoint of toner durability and charge stability. Furthermore, it is more preferably 0.88 to 0.93. The average circularity of the fine particles can be increased by raising the reaction temperature and lengthening the reaction time in the polymerization condensation process. Conversely, the average circularity of the fine particles can be decreased by lowering the reaction temperature and shortening the reaction time in the polymerization condensation process.

[0074] The toner additive preferably contains the above-mentioned fine particles. The toner comprises toner particles and the toner additive, wherein the toner particles contain a binder resin, and the toner additive is the above-mentioned fine particles. From the viewpoint of electrostatic stability, the amount of the toner additive in the toner is preferably 0.1 to 20.0 parts by mass per 100 parts by mass of toner particles. More preferably 0.2 to 18.0 parts by mass, even more preferably 0.5 to 15.0 parts by mass, and even more preferably 1.0 to 10.0 parts by mass.

[0075] When the toner additive content is 0.1 parts by mass or more, stress on the toner can be suppressed even when printing a large number of low-density images for a long period of time in harsh environments such as high temperature and high humidity, thereby improving durability and static charge stability. Furthermore, when the toner additive content is 20.0 parts by mass or less, filming of additive particles onto the carrier and photosensitive material can be suppressed even when printing high-density images for a long period of time.

[0076] <Binding resin> The binder resin used in toner is not particularly limited, and the following polymers can be used. For example, monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene copolymers such as styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylate methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, and styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural resin-modified phenol resin, natural resin-modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral resin, terpene resin, coumarone-indene resin, and petroleum-based resins. Among these, polyester resin is preferred from the viewpoint of durability and electrostatic stability.

[0077] Furthermore, from the viewpoint of environmental stability and electrostatic stability, it is preferable that the acid value of the polyester resin is 0.5 mg KOH / g to 40 mg KOH / g. The functional group that generates the acid value in the polyester resin and the Si-R in the external additive. 1 These interact, affecting durability and toner charging in high-temperature, high-humidity environments. The properties can be further improved. The acid value is more preferably 1 mg KOH / g to 20 mg KOH / g, and even more preferably 1 mg KOH / g to 15 mg KOH / g.

[0078] <Coloring agent> Toner particles may contain colorants. Examples of colorants include: Black colorants include carbon black; and black tones produced by mixing yellow, magenta, and cyan colorants. While pigments may be used alone as colorants, it is preferable to use dyes and pigments in combination to improve clarity, which is preferable in terms of full-color image quality.

[0079] The following are examples of pigments used for magenta toner: CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0080] Examples of dyes for magenta toner include: oil-soluble dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Violet 1; 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, 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0081] Examples of pigments for cyan toner include: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Bat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted onto the phthalocyanine skeleton. CI Solvent Blue 70 is an example of a dye for cyan toner.

[0082] Examples of pigments for yellow toner include: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Bat Yellow 1, 3, 20. CI Solvent Yellow 162 is an example of a dye for yellow toner. The colorant content is preferably 0.1 parts by mass or more and 30 parts by mass or less per 100 parts by mass of binder resin.

[0083] <wax> Wax may be used in the toner particles. Examples of waxes include: hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax; waxes that partially or completely remove fatty acid esters such as deoxidized carnauba wax. Oxidized.

[0084] Furthermore, the following can be mentioned: saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melicyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melicyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearate amide, ethylenebiscaprate amide, ethylenebislaurate amide, and hex Saturated fatty acid bisamides such as methylene bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'dioleyl adipamide, and N,N'dioleyl sebacinamide; aromatic bisamides such as m-xylene bisstearamide and N,N'distearyl isophthalamide; fatty acid metal salts (generally called metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes with vinyl monomers such as styrene or acrylic acid; partially esterified fatty acids and polyhydric alcohols such as behenic acid monoglyceride; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils. The wax content is preferably 2.0 to 30.0 parts by mass per 100 parts by mass of binder resin.

[0085] <Charge control agent> The toner particles may contain a charge control agent as needed. While known charge control agents can be used, aromatic carboxylic acid metal compounds are particularly preferred, as they are colorless, have a fast toner charging speed, and can stably maintain a constant charge level.

[0086] Examples of negative charge control agents include salicylate metal compounds, naphthoate metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid as a side chain, polymer compounds having sulfonate salts or sulfonic acid esters as a side chain, polymer compounds having carboxylate salts or carboxylic acid esters as a side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0087] Examples of positive charge control agents include quaternary ammonium salts, polymeric compounds having the quaternary ammonium salt in their side chains, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The amount of charge control agent added is preferably 0.2 to 10 parts by mass per 100 parts by mass of the binder resin.

[0088] <Inorganic fine particles> In addition to the toner additives mentioned above, the toner may contain other inorganic fine particles as needed. The inorganic fine particles may be added internally to the toner particles or mixed with the toner particles as an external additive. When included as an external additive, inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles are preferred. The inorganic fine particles are preferably hydrophobized with a hydrophobic agent such as a silane compound, silicone oil, or a mixture thereof.

[0089] As an external additive for improving fluidity, it has a specific surface area of ​​50 m². 2 / g or more 400m 2 Inorganic fine particles of less than / g are preferred. To achieve both improved fluidity and stable durability, inorganic fine particles with a specific surface area within the above range may be used in combination with the toner additive.

[0090] The inorganic fine particles described above are preferably used in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of toner particles. When this range is met, the effect of electrostatic stability is easily obtained. The content of the aforementioned toner additive is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, and even more preferably 90% to 100% by mass of the total additive.

[0091] <Developer> Toner can be used as a one-component developer, but to further improve dot reproduction and to supply stable images over a long period of time, it can also be mixed with a magnetic carrier and used as a two-component developer. That is, a two-component developer containing toner and a magnetic carrier is preferable, wherein the toner is the toner described above.

[0092] As magnetic carriers, generally known materials can be used, such as iron oxide, unoxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, their alloy particles, and their oxide particles; magnetic materials such as ferrite; and magnetic material dispersion resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state. The mixing ratio of the magnetic carrier to the toner is preferably such that the toner concentration in the two-component developer is 2% by mass or more and 15% by mass or less, and more preferably 4% by mass or more and 13% by mass or less.

[0093] <Method for manufacturing toner particles> The method for producing toner particles is not particularly limited, and known production methods such as suspension polymerization, emulsification agglutination, melt kneading, and dissolution suspension can be employed. The obtained toner particles can be mixed with the above-mentioned toner additive and, if necessary, other additives to produce toner.

[0094] Mixing of toner particles and external additives can be done using mixing equipment such as a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.), or Novilta (manufactured by Hosokawa Micron Corporation).

[0095] The following describes methods for measuring various physical properties. <Separation of fine particles (external additives for toner) and toner particles from toner> The physical properties of toner can also be measured using fine particles separated by the following method: Add 200g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100mL of deionized water and dissolve it in a water bath to prepare a concentrated sucrose solution. Place 31g of this concentrated sucrose solution and 6mL of Contaminon N (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) into a centrifuge tube to prepare a dispersion. Add 1g of toner to this dispersion and break up any clumps of toner with a spatula or similar tool.

[0096] The centrifugation tube is shaken for 20 minutes at a rate of 350 strokes per minute using a shaker (Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX)). After shaking, the solution is transferred to a glass tube for a swing rotor (50 mL), and centrifugation is performed in a centrifuge at 3500 rpm for 30 minutes. After centrifugation, toner particles are present in the uppermost layer of the glass tube, while fine particles are present in the lower aqueous solution layer. The lower aqueous solution is collected and centrifuged to separate the sucrose from the fine particles, and the fine particles are collected. If necessary, centrifugation is repeated to ensure sufficient separation, then the dispersion is dried and the fine particles are collected. If multiple fine particles are added, the fine particles can be separated using methods such as centrifugation. It is possible.

[0097] <Method for measuring the number-average particle size of primary particles in fine particles> The number-average particle size of primary particles in microparticles can be determined by centrifugal sedimentation. Specifically, 0.01 g of dried microparticles are placed in a 25 ml glass vial, and a solution is prepared by adding 0.2 g of 5% Triton solution and 19.8 g of RO water. Next, the probe (the very tip) of an ultrasonic disperser is immersed in the above solution, and ultrasonic dispersion is obtained by ultrasonic dispersion at an output of 20 W for 15 minutes. Subsequently, this dispersion is used in the CPS Instrument The number-average particle size of primary particles was measured using a centrifugal sedimentation particle size distribution analyzer DC24000 from company S. The disk rotation speed was set to 18000 rpm, and the true density was 1.3 g / cm³. 3 Set the parameters accordingly. Before measurement, calibrate the device using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0098] <Method for measuring the acid value of resins such as binder resins> Acid value is the amount of potassium hydroxide (in mg) required to neutralize the acidic components, such as free fatty acids and resin acids, contained in 1 g of sample. Acid value is measured according to JIS-K0070-1992 as follows.

[0099] (1) Reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add deionized water to make a total volume of 100 mL, and obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95 vol%) to make 1 L. Place the solution in an alkali-resistant container, taking care not to allow it to come into contact with carbon dioxide, etc., and leave it for 3 days. After that, filter the solution to obtain potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by taking 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and determining the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used should be prepared in accordance with JIS K 8001-1998.

[0100] (2) Operation (A) Main examination 2.0 g of the pulverized sample is accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a toluene / ethanol (2:1) mixture is added. The sample is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and the sample is titrated with the potassium hydroxide solution. The titration endpoint is reached when the indicator turns a pale pink color for approximately 30 seconds. (B) Blank test The titration procedure is the same as described above, except that no sample is used (i.e., only a mixed solution of toluene / ethanol (2:1) is used). (3) Substitute the obtained results into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S Here, A: acid value (mgKOH / g), B: volume of potassium hydroxide solution added in the blank test (mL), C: volume of potassium hydroxide solution added in the main test (mL), f: factor of the potassium hydroxide solution, and S: mass of the sample (g).

[0101] <Measurement of the acid value of polyester resin from toner> The following method can be used to measure the acid value of polyester resin in toner. Separation of polyester resin from toner and measurement of the acid value are performed using the following method: Dissolve the toner in tetrahydrofuran (THF), and remove the solvent from the resulting soluble matter under reduced pressure to obtain the tetrahydrofuran (THF) soluble component of the toner. Dissolve the obtained tetrahydrofuran (THF) soluble component of the toner in chloroform to prepare a sample solution with a concentration of 25 mg / ml. The obtained sample solution (3.5 ml) is poured into the apparatus described below, and under the conditions described below, the component with a molecular weight of 2000 or more is separated as the resin component. Preparative GPC device: Preparative HPLC LC-980 model manufactured by Japan Analytical Industry Co., Ltd. Preparative columns: JAIGEL 3H, JAIGEL 5H (manufactured by Japan Analytical Industry Co., Ltd.) Eluent: Chloroform Flow rate: 3.5ml / min After separating the high molecular weight components derived from the resin, the solvent is removed by distillation under reduced pressure, and the mixture is then dried under reduced pressure in a 90°C atmosphere for 24 hours. The above procedure is repeated until approximately 2.0 g of the resin component is obtained. The acid value of the obtained sample is measured according to the procedure described above.

[0102] <Method for measuring the weight-average particle size (D4) of toner particles> The weight-average particle size (D4) of toner particles is measured using the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter), a precision particle size distribution analyzer using the pore electrical resistance method with a 100 μm aperture tube, and the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data, with an effective measurement channel count of 25,000. The measurement data is then analyzed and calculated. The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to a concentration of approximately 1% by mass; for example, "ISOTON II" (manufactured by Beckman Coulter) can be used. Before performing the measurement and analysis, the dedicated software should be configured as follows.

[0103] In the "Change Standard Measurement 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 the value obtained using "standard particle 10.0 μm" (manufactured by Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flush on the aperture tube after measurement. In the "Pulse to Particle Size Conversion Settings" screen of the dedicated software, set the bottle spacing to logarithmic particle size, the particle size bottle to 256 particle size bottle, and the particle size range to 2 μm or more and 60 μm or less. The specific measurement method is as follows.

[0104] (1) Pour approximately 200 ml of the electrolytic solution into a 250 ml round-bottom glass beaker specifically designed for the Multisizer 3, set it on the sample stand, and stir the mixture with the stirrer rod at 24 revolutions per second in a counterclockwise direction. Then, use the "Aperture Tube Flash" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Place approximately 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottomed glass beaker, and add approximately 0.3 ml of a diluted solution of "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted three times by mass with deionized water as a dispersant. (3) Two oscillators with an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and a predetermined amount of deionized water is placed in the water tank of an ultrasonic dispersion device called "Ultrasonic Dispersion System Tetora150" (manufactured by Nikko Bios Co., Ltd.) with an electrical output of 120 W. Approximately 2 ml of the aforementioned Contaminon N is added to this water tank. (4) Place the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic aqueous solution inside the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) with ultrasound, add approximately 10 mg of toner particles to the electrolytic aqueous solution in small amounts and disperse them. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank to be between 10°C and 40°C as appropriate. (6) Using a pipette, the electrolytic aqueous solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the concentration is adjusted to approximately 5%. The measurement is then continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software attached to the device, and the weight-average particle size (D4) is calculated. Note that the "Average Diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen when the dedicated software is set to Graph / Volume % is the weight-average particle size (D4).

[0105] <Method for measuring the average circularity of fine particles> Average circularity is used as a simple method to quantitatively represent the shape of a particle. Using a Sysmex FPIA-3000 flow-type particle image analyzer, particles with an equivalent circle diameter in the range of 0.01 μm to 400 μm were measured. The circularity of the measured particles was calculated using the following formula, and the average circularity was defined as the sum of the circularities of the measured particles divided by the total number of particles. The number of particles measured was assumed to be 5000. Circularity a = L0 / L (In the formula, L0 represents the perimeter of a circle with the same projected area as the particle image, and L represents the perimeter of the particle projection image when the image is processed with an image processing resolution of 512 × 512 (0.3 μm × 0.3 μm pixels).)

[0106] <Method for measuring the Young's modulus of fine particles> The Young's modulus of microparticles is determined from microcompression tests using a Hyditron PI 85L picoindenter (BRUKER). The Young's modulus (MPa) is calculated from the slope of the profile (load-displacement curve) obtained from the displacement (nm) and test force (μN) obtained from the measurement. • Equipment and jigs Base system: Hysitron PI-85L Measuring indenter: 1 μm flat-end indenter SEM used: Thermo Fisher Versa 3D SEM conditions: -10°tilt, 13pA at 10keV • Measurement conditions Measurement mode: Displacement control Maximum displacement: 30nm Displacement speed: 1 nm / second Hold time: 2 seconds Unloading speed: 5nm / sec ·Analysis method Hertz analysis is applied to the obtained load-displacement curves for compression from 0 nm to 10 nm to calculate the Young's modulus of the microparticles. • Sample adjustment A silicon wafer on which fine particles are attached.

[0107] <Solid 29 Method for measuring the abundance ratio and B / A ratio of constituent compounds in fine particles using Si-NMR solid 29 In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional group bound to Si in the constituent compounds of the nanoparticles. By identifying each peak position using a standard sample, the structure bound to Si can be determined. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak areas. The ratio of the peak areas of Q-unit structures, T-unit structures, and D-unit structures to the total peak area can be calculated.

[0108] solid 29 The specific measurement conditions for Si-NMR are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DDMAS method 29 Si 45° Sample tube: Zirconia 3.2mmφ Sample: Filled in a test tube in powder form. Sample rotation speed: 10kHz Relaxation delay: 180s Scan: 2000

[0109] After the measurement, the multiple silane components of the sample with different substituents and bonding groups are separated into peaks for the following M, D, T, and Q unit structures by curve fitting, and the peak area of ​​each is calculated. M unit structure: (Ra)(Rb)(Rc)SiO 1 / 2 (S1) D unit structure: (Rd)(Re)Si(O 1 / 2 )2(S2) T unit structure: RfSi(O 1 / 2 )3(S3) Q Unit structure: Si(O) 1 / 2 )4(S4) Let (S1+S2+S3+S4)=SA.

[0110] In the formulas (S1), (S2) and (S3), Ra, Rb, Rc, Rd, Re, and Rf each represent an organic group bonded to silicon, such as a hydrocarbon group having 1 to 6 carbon atoms (e.g., an alkyl group), or a halogen atom. When it is necessary to confirm the structure in further detail, 29 together with the measurement results of Si-NMR 13 C-NMR and 1 the measurement results of H-NMR may also be used in combination for identification. S2 / SA, S3 / SA and S4 / SA are calculated from SA, S2, S3, and S4 obtained in this manner.

[0111] (Calculation method for B / A) Solid 29 From the chart obtained by Si-NMR, the peak area of (Si-R 1 ) in each unit structure at the following positions is calculated. R 1 is as described above, and represents an alkyl group having 1 to 6 carbon atoms. (Si-R 1 )-containing Q4 unit structure has a peak area of S44, (Si-R 1 )-containing Q3 unit structure has a peak area of S43, (Si-R 1 )-containing Q2 unit structure has a peak area of S42, and (Si-R 1 )-containing Q1 unit structure has a peak area of S41. (Si-R 1 )-containing T3 unit structure has a peak area of S33, (Si-R 1 )-containing T2 unit structure has a peak area of S32, and (Si-R 1 )-containing T1 unit structure has a peak area of S31. (Si-R 1 )-containing D2 unit structure having one (Si-R) has a peak area of S22A, (Si-R 1 )-containing D2 unit structure having two (Si-R) has a peak area of S22B, (Si-R 1 )-containing D1 unit structure having one (Si-R) has a peak area of S21A, and (Si-R 1 )-containing D1 unit structure having two (Si-R) has a peak area of S21B. (Si-R 1 )-containing M1 unit structure having one (Si-R) has a peak area of S11A, (Si-R 1The peak area of ​​the M1 unit structure having two of these is S11B, (Si-R 1 Let S11C be the peak area of ​​the M1 unit structure that has three of these.

[0112] At this time, the Si-R in each unit structure is as follows: 1 Calculate the peak area ratio. SiR corresponding to the Q unit structure 1 The peak area ratio QB = (S44 / S4) × 0 + (S43 / S4) × 0 + (S42 / S4) × 0 + (S41 / S4) × 0 SiR corresponding to T-unit structure 1 Peak area ratio TB = (S33 / S3) × 1 / 4 + (S32 / S3) × 1 / 4 + (S31 / S3) × 1 / 4 Si-R corresponding to D-unit structure 1 Peak area ratio DB = (S22A / S2) × 1 / 4 + (S22B / S2) × 1 / 2 + (S21A / S2) × 1 / 4 + (S21B / S2) × 1 / 2 SiR corresponding to M-unit structure 1 Peak area ratio MB = (S11A / S1) × 1 / 4 + (S11B / S1) × 1 / 2 + (S11C / S1) × 3 / 4

[0113] The constituent 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 this disclosure, the difference in the degree of condensation in each unit is distinguished by the number of crosslinking oxygen groups, such as D1 units, D2 units, T1 units, T2 units, T3 units, etc. That is, the numbers following the letters such as D and T indicate the number of crosslinking oxygen groups that form siloxane bonds. For example, a T3 unit indicates that all three functional groups are condensed and involved in siloxane bonding. A T2 unit indicates that two of the three functional groups are condensed and involved in siloxane bonding, while one functional group is not condensed.

[0114] Q Unit Structure Q4: -105ppm to -115ppm Q3: -95ppm to -104ppm Q2: -85ppm to -94ppm Q1: -75ppm to -84ppm T-unit structure T3: -60ppm to -70ppm T2: -50ppm to -59ppm T1: -40ppm to -49ppm D Unit Structure D2: -15ppm to -25ppm D1: -10ppm to -14ppm M-unit structure M1: -5ppm to -9ppm From the above formula, B / A=QB×S4 / SA+TB×S3 / SA+DB×S2 / SA+MB×S1 / SA Calculate.

[0115] <Method for measuring the degree of hydrophobicity of fine particles> The degree of hydrophobicity of fine particles is calculated by methanol titration. Specifically, it is measured using the following procedure: 0.5 g of toner additive particles are added to 50 ml of RO water. Methanol is added dropwise from a burette to the mixture while stirring the mixture until the entire amount of toner additive particles is wet. Whether the entire amount is wet is determined by whether all the fine particles that were suspended on the surface of the water have sunk into the liquid and are suspended in the liquid. At this time, the percentage of methanol (by volume) relative to the total amount of the mixture and methanol added at the end of the titration is defined as the degree of hydrophobicity. A higher degree of hydrophobicity indicates higher hydrophobicity.

[0116] <Method for measuring surface treatment agents in fine particles> The surface treatment agent for the fine particles is analyzed by pyrolysis GC-MS (gas chromatography-mass spectrometry). The measurement conditions are specifically as follows: Equipment: GC6890A (Agilent), pyrolysis unit (Nippon Analytical Engineering Co., Ltd.) Column: HP-5ms 30m Thermal decomposition temperature: 590℃ By identifying the position of each peak in the profile obtained through measurement using a standard sample, the surface treatment agent for the fine particles is identified.

[0117] <Measurement of volume-average pore diameter and total pore volume of fine particles> The volume-average pore diameter and total pore volume of the microparticles are measured using a Tristar3000 pore distribution analyzer (manufactured by Shimadzu Corporation) by gas adsorption, which involves adsorbing nitrogen gas onto the sample surface. The measurement method follows the operation manual issued by Shimadzu Corporation. First, 0.5 g of the sample is placed in a sample tube and vacuumed at 100°C for 24 hours. After vacuuming is complete, the sample weight is accurately measured to obtain the sample. From the obtained sample, the volume-average diameter of the pores and the total pore volume in the range of pore diameters from 1.7 nm to 300.0 nm can be determined using the BJH method with the pore distribution analyzer described above. The density value required for measurement is the true density value measured using the dry densimeter Accupic 1330 (manufactured by Shimadzu Corporation).

[0118] <Measurement of BET specific surface area of ​​fine particles> The BET specific surface area Y can be determined by the BET method (specifically, the BET multipoint method) using a low-temperature gas adsorption method with a dynamic constant-pressure approach. Nitrogen gas is adsorbed onto the sample surface using a specific surface area measuring device (product name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation). By measuring using the BET multipoint method, the BET specific surface area Y(m²) can be determined. 2 It is possible to calculate ( / g). In the formula below, the unit of "average circle equivalent diameter" is "m". Also, the theoretical BET specific surface area X(m 2 The value per g is calculated by assuming that the particles are perfectly spherical and using the following formula. Theoretical BET specific surface area X= (4 × π × (「 Average circle equivalent diameter A 」 / 2) 2 ) / (4 / 3×π× (「 Average circle equivalent diameter A 」 / 2) 3 × density)×1000 000 Density required for calculation ( g / cm 3The value of ) is the true density measured using a dry densimeter, AccuPic 1330 (manufactured by Shimadzu Corporation). In addition, the value obtained from the measurement of the number-average particle size of the primary particles of the fine particles as described above is used as the average circular equivalent diameter A of the fine particles.

[0119] <Method for measuring the elemental concentration (dC) of carbon atoms in fine particles> XPS is used to measure the elemental ratios present in fine particles. The elemental concentrations of silicon (dSi), oxygen (dO), and carbon (dC) are defined as dSi, and their sum is set to 100.0 atomic%, at which point the concentration of dC is calculated. The XPS measurement conditions are described below. Equipment used: ULVAC-PHI PHI5000VersaProbeII Irradiation: Al-Kα radiation Beam diameter: 100 μm Output: 25W 15kV Photoelectron acquisition angle: 45° PassEnergy: 58.70eV Stepsize: 0.125eV XPS peaks: C2p, O2p, Si2p Measurement range: 300 μm × 200 μm Gun Type: GCIB Time: 15 min Interval: 1 min SputterSetting: 20kV The sample is placed in a sample setting hole with a diameter of 2 mm and a depth of 2 mm, which is machined on the platen specifically for XPS. [Examples]

[0120] The present invention will be specifically described by the following examples. However, these examples do not limit the present invention in any way. Unless otherwise specified, all "parts" in the following formulations are based on mass.

[0121] <Example of manufacturing of fine particles 1> 1. Hydrolysis process In a 200ml beaker, add 43.2g of RO water and 0.008g of acetic acid as a catalyst, and 4 The mixture was stirred at 5°C. 27.2 g of tetraethoxysilane and 27.2 g of dimethyldimethoxysilane were added and stirred for 1.5 hours to obtain the starting material solution.

[0122] 2. Polycondensation process In a 1000 ml beaker, 68.8 g of RO water, 340.0 g of methanol, and 2.0 g of 28% aqueous ammonia were added and stirred at 30°C to prepare an alkaline aqueous medium. To this alkaline aqueous medium, the raw material solution obtained in step 1 (hydrolysis) was added dropwise over 1 minute. The mixture after the addition of the raw material solution was stirred at 20°C for 1.0 hour to allow the polycondensation reaction to proceed and obtain the polycondensation reaction solution.

[0123] 3.Particleization process 1000g of RO water was placed in a 2000ml beaker, and the polycondensation reaction solution obtained in step 2 (condensation polymerization) was added dropwise over 10 minutes while stirring at 25°C. The mixture was heated to 40°C and stirred at 40°C for 1.0 hour to obtain a dispersion containing silicon polymer particles having siloxane bonds.

[0124] 4. Hydrophobization process 3. To a dispersion containing silicon polymer particles having siloxane bonds obtained in the particle formation step, 27.1 g of hexamethyldisilazane was added as a hydrophobic agent, and the mixture was stirred at 60°C for 2.5 hours. After standing for 5 minutes, the powder that settled at the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain fine particles 1. The number-average primary particle size of fine particles 1 was 0.12 μm. The total pore volume of fine particles 1 was 0.45 cm³. 3 The value was / g. The physical properties of particle 1 are shown in Table 1.

[0125] <Example of manufacturing of fine particles 2> Fine particles 2 were obtained in the same manner as in the production example of fine particles 1, except that the amount of hexamethyldisilazane used in the hydrophobication step was changed to 16.3 g. The physical properties of the obtained fine particles 2 are shown in Table 1.

[0126] <Example of manufacturing of fine particles 3> Fine particles 3 were obtained in the same manner as in the production example of fine particles 1, except that the amount of hexamethyldisilazane used in the hydrophobication step was changed to 37.9 g. The physical properties of the obtained fine particles 3 are shown in Table 1.

[0127] <Example of manufacturing of fine particles 4> Fine particles 4 were obtained in the same manner as in the production example of fine particles 3, except that the stirring temperature was changed to 70°C during the hydrophobicization process. The physical properties of the obtained fine particles 4 are shown in Table 1.

[0128] <Example of manufacturing of fine particles 5> Fine particles 5 were obtained in the same manner as in the production example of fine particles 2, except that the stirring temperature was changed to 50°C during the hydrophobicization process. The physical properties of the obtained fine particles 5 are shown in Table 1.

[0129] <Example of manufacturing of fine particles 6> Fine particles 6 were obtained in the same manner as in the production example of fine particles 1, except that the stirring time of the mixed solution after the addition of the raw material solution in the condensation polymerization process was changed to 0.5 hours. The physical properties of the obtained fine particles 6 are shown in Table 1.

[0130] <Example of manufacturing of fine particles 7> Fine particles 7 were obtained in the same manner as in the production example of fine particles 1, except that the stirring time of the mixed solution after the addition of the raw material solution in the condensation polymerization process was changed to 1.5 hours. The physical properties of the obtained fine particles 7 are shown in Table 1.

[0131] <Example of manufacturing of fine particles 8> In the condensation polymerization process, fine particles 8 were obtained in the same manner as in the production example of fine particles 1, except that the stirring temperature of the mixed solution after the addition of the raw material solution was changed to 15°C and the stirring time was changed to 0.5 hours. The physical properties of the obtained fine particles 8 are shown in Table 1.

[0132] <Example of manufacturing of fine particles 9> In the condensation polymerization process, fine particles 9 were obtained in the same manner as in the production example of fine particles 1, except that the stirring temperature of the mixed solution after the addition of the raw material solution was changed to 25°C and the stirring time was changed to 1.5 hours. The physical properties of the obtained fine particles 9 are shown in Table 1.

[0133] <Example of manufacturing of fine particles 10> Fine particles 10 were obtained in the same manner as in the production example of fine particles 1, except that the hydrophobic agent used in the hydrophobicization process was changed to octamethylcyclotetrasiloxane. The physical properties of the obtained fine particles 10 are shown in Table 1.

[0134] <Example of manufacturing of fine particles 11> Fine particles 11 were obtained in the same manner as in the production example of fine particles 1, except that the hydrophobic agent used in the hydrophobicization process was changed to chlorotrimethylsilane. The physical properties of the obtained fine particles 11 are shown in Table 1.

[0135] <Example of manufacturing of fine particles 12> Fine particles 12 were obtained in the same manner as in the production example of fine particles 1, except that the hydrophobic agent used in the hydrophobication process was changed to trifluoropropyltrimethoxysilane. The physical properties of the obtained fine particles 12 are shown in Table 1.

[0136] <Example of manufacturing of fine particles 13> Fine particles 13 were obtained in the same manner as in the production example of fine particles 1, except that the hydrophobic agent used in the hydrophobicization process was changed to dodecyltrimethoxysilane. The physical properties of the obtained fine particles 13 are shown in Table 1.

[0137] <Example of manufacturing of fine particles 14> Fine particles 14 were obtained in the same manner as in the production example of fine particles 1, except that a hydrophobic agent was not added in the hydrophobicization process. The physical properties of the obtained fine particles 14 are shown in Table 1.

[0138] <Example of manufacturing of fine particles 15> Fine particles 15 were obtained in the same manner as in the production example of fine particles 14, except that tetraethoxysilane was changed to 38.1 g and dimethyldimethoxysilane to 16.3 g in the hydrolysis step. The physical properties of the obtained fine particles 15 are shown in Table 1.

[0139] <Example of manufacturing of fine particles 16> Fine particles 16 were obtained in the same manner as in the production example of fine particles 14, except that in the hydrolysis step, tetraethoxysilane was changed to 16.3 g, trimethoxymethylsilane to 27.2 g, and dimethyldimethoxysilane to 10.9 g. The physical properties of the obtained fine particles 16 are shown in Table 1.

[0140] <Example of manufacturing of fine particles 17> Fine particles 17 were obtained in the same manner as in the production example of fine particles 14, except that the amount of tetraethoxysilane was changed to 43.5 g and dimethyldimethoxysilane to 10.9 g in the hydrolysis step. The physical properties of the obtained fine particles 17 are shown in Table 1.

[0141] <Example of manufacturing of fine particles 18> In the hydrolysis process, 16.3 g of tetraethoxysilane and trimethoxymethylsilane were added. Fine particles 18 were obtained in the same manner as in the production example of fine particles 14, except that the amount of n was changed to 24.5 g and dimethyldimethoxysilane to 13.6 g. The physical properties of the obtained fine particles 18 are shown in Table 1.

[0142] <Example of manufacturing of fine particles 19> Fine particles 19 were obtained in the same manner as in the production example of fine particles 9, except that the stirring temperature was changed to 50°C in the particle formation process and no hydrophobic agent was added in the hydrophobicization process. The physical properties of the obtained fine particles 19 are shown in Table 1.

[0143] <Example of manufacturing of fine particles 20> Fine particles 20 were obtained in the same manner as in the production example of fine particles 8, except that the stirring temperature was changed to 30°C in the particle formation process and no hydrophobic agent was added in the hydrophobicization process. The physical properties of the obtained fine particles 20 are shown in Table 1.

[0144] <Example of manufacturing of fine particles 21> Fine particles 21 were obtained in the same manner as in the production example of fine particles 19, except that the amount of 28% aqueous ammonia added in the condensation polymerization process was changed to 2.5 g. The physical properties of the obtained fine particles 21 are shown in Table 1.

[0145] <Example of manufacturing of fine particles 22> Fine particles 22 were obtained in the same manner as in the production example of fine particles 20, except that the amount of 28% aqueous ammonia added in the condensation polymerization process was changed to 1.0 g. The physical properties of the obtained fine particles 22 are shown in Table 1.

[0146] <Example of manufacturing of fine particles 23> Fine particles 23 were obtained in the same manner as in the production example of fine particles 14, except that 108.8 g of RO water and 300.0 g of methanol were used in the condensation polymerization process. The physical properties of the obtained fine particles 23 are shown in Table 1.

[0147] <Example of manufacturing of fine particles 24> Fine particles 24 were obtained in the same manner as in the production example of fine particles 14, except that 28.8 g of RO water and 380.0 g of methanol were used in the condensation polymerization process. The physical properties of the obtained fine particles 24 are shown in Table 1.

[0148] <Example of manufacturing of fine particles 25> Fine particles 25 were obtained in the same manner as in the production example of fine particles 23, except that the amount of 28% aqueous ammonia added in the condensation polymerization process was changed to 2.5 g. The physical properties of the obtained fine particles 25 are shown in Table 1.

[0149] <Example of manufacturing of fine particles 26> Fine particles 26 were obtained in the same manner as in the production example of fine particles 24, except that the amount of 28% aqueous ammonia added in the condensation polymerization process was changed to 1.5 g. The physical properties of the obtained fine particles 26 are shown in Table 1.

[0150] <Example of manufacturing of fine particles 27> In the hydrolysis process, fine particles 27 were obtained in the same manner as in the production example of fine particles 14, except that the stirring time was changed to 2.0 hours and the stirring temperature to 50°C. The physical properties of the obtained fine particles 27 are shown in Table 1.

[0151] <Example of manufacturing of fine particles 28> In the hydrolysis process, the stirring time was set to 1.0 hour and the stirring temperature to 40°C, and the condensation polymerization process was carried out. Except for changing the amount of 28% ammonia water used to 2.5g, fine particles 28 were obtained in the same manner as in the production example of fine particles 14. The physical properties of the obtained fine particles 28 are shown in Table 1.

[0152] <Example of manufacturing of fine particles 29> Fine particles 29 were obtained in the same manner as in the production example of fine particles 27, except that the amount of acetic acid added in the hydrolysis process was changed to 0.005 g. The physical properties of the obtained fine particles 29 are shown in Table 1.

[0153] <Example of manufacturing of fine particles 30> Fine particles 30 were obtained in the same manner as in the production example of fine particles 28, except that the amount of acetic acid added in the hydrolysis process was changed to 0.010 g. The physical properties of the obtained fine particles 30 are shown in Table 1.

[0154] <Example of manufacturing of fine particles 31> Fine particles 31 were obtained in the same manner as in the production example of fine particles 1, except that tetraethoxysilane and dimethyldimethoxysilane were not added in the hydrolysis step, and instead 54.4 g of trimethoxymethylsilane was added, and the stirring temperature was changed to 30°C and the stirring time to 0.5 hours. The physical properties of the obtained fine particles 31 are shown in Table 1.

[0155] <Example of manufacturing of fine particles 32> Except for changing the amount of tetraethoxysilane to 16.3 g and dimethyldimethoxysilane to 38.1 g in the hydrolysis step, and performing the hydrophobicization step as in the case of fine particle 1, fine particle 32 was obtained in the same manner as in the production example of fine particle 22. The physical properties of the obtained fine particle 32 are shown in Table 1.

[0156] <Example of manufacturing of fine particles 33> In a 2000 ml beaker, 124.0 g of ethanol, 24.0 g of RO water, and 10.0 g of 28% aqueous ammonia were added. The temperature of this solution was adjusted to 70°C, and 232.0 g of tetraethoxysilane and 84.0 g of 5.4% aqueous ammonia were added dropwise over 0.5 hours while stirring. After the addition was complete, stirring was continued for another 0.5 hours to perform hydrolysis, thereby obtaining a dispersion of silicon polymer particles having siloxane bonds. To the dispersion of silicon polymer particles having siloxane bonds obtained in the above step, 150.0 g of hexamethyldisilazane was added at room temperature. The dispersion was then heated to 50-60°C and stirred for 3.0 hours. The powder in the dispersion was recovered by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain fine particles 33. The physical properties of the obtained fine particles 33 are shown in Table 1.

[0157] <Example of manufacturing of fine particles 34> Fine particles 34 were obtained in the same manner as in the production example of fine particles 1, except that in the condensation polymerization step, the stirring time of the mixed solution after the addition of the raw material solution was changed to 1.5 hours and the stirring temperature was changed to 30°C, and in the particle formation step, the stirring temperature was changed to 25°C and the stirring time to 0.5 hours. The physical properties of the obtained fine particles 34 are shown in Table 1.

[0158] [Table 1] In the table, pore volume represents the total pore volume, and pore diameter represents the volume-average diameter of the pores. Particle size is the number-average particle size of the primary particles, and circularity is the average circularity. Hydrophobicity is expressed in volume percent.

[0159] <Example of Polyester Resin A1 Production> • Polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 moles) Terephthalic acid (TPA) 25.0 parts (0.145 moles) • Adipic acid 8.0 parts (0.054 moles) Titanium tetrabutoxide 0.5 part The above materials were placed in a 4-liter four-necked glass flask, and a thermometer, stirring rod, condenser, and nitrogen inlet tube were attached and placed inside a mantle heater. Next, the flask was purged with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was then reacted at 200°C for 4 hours while stirring (first reaction step). Subsequently, 1.2 parts (0.006 mol) of trimellitic anhydride (TMA) was added, and the mixture was reacted at 180°C for 1 hour (second reaction step) to obtain polyester resin A1. The acid value of this polyester resin A1 was 5 mg KOH / g.

[0160] <Example of Polyester Resin A2 Manufacturing> • Polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts (0.155 moles) Terephthalic acid 24.1 parts (0.145 moles) Titanium tetrabutoxide 0.6 parts The above materials were placed in a 4-liter, four-necked glass flask, and a thermometer, stirring rod, condenser, and nitrogen inlet tube were attached and placed inside a mantle heater. Next, the flask was purged with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was then reacted at 200°C for 2 hours while stirring. After that, 5.8 parts (0.030 mol%) 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 this polyester resin A2 was 10 mg KOH / g.

[0161] <Example of toner particle 1 manufacturing> • Polyester resin A1 70.0 parts • Polyester resin A2 30.0 parts Fischer-Tropsch wax (peak temperature of maximum endothermic peak: 78°C) 5.0 parts CI Pigment Blue 15:3 5.0 parts 0.1 part of 3,5-di-t-butylsalicylate aluminum compound The raw materials shown in the above formula were mixed using a Henschel mixer (FM-75 model, manufactured by Nippon Coke Industries Co., Ltd.) at a rotation speed of 20 seconds. -1After mixing for 5 minutes of rotation, the mixture was kneaded in a twin-screw kneader (model PCM-30, manufactured by Ikegai Corp.) set to a temperature of 125°C and a rotation speed of 300 rpm. The obtained kneaded product was cooled, coarsely pulverized to a diameter of 1 mm or less with a hammer mill, and a coarsely pulverized product was obtained. The obtained coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund-Turbo Corporation).

[0162] Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were set such that the rotation speed of the classification rotor was 50.0 s -1 for the classification. The obtained toner particles 1 had a weight average particle diameter (D4) of 5.9 μm.

[0163] <Production Example of Toner 1> · 100 parts of Toner Particles 1 · 6.0 parts of Fine Particles 1 The above materials were processed in a Henschel mixer model FM-10C (manufactured by Mitsui Miike Machinery Co., Ltd.) at a rotation speed of 30 s -1 and mixed for a rotation time of 10 minutes to obtain Toner 1.

[0164] <Production Examples of Toners 2 to 38> Toners 2 to 38 were produced in the same manner as in Production Example of Toner 1, except that the type and addition amount of fine particles were changed to those described in Table 2.

Table 2

[0165] <Production Example of Carrier 1> · Magnetite 1 having a number average particle diameter of 0.30 μm and a magnetization intensity of 65 Am under a magnetic field of (1000 / 4π (kA / m) 2 / kg) · Magnetite 2 having a number average particle diameter of 0.50 μm and a magnetization intensity of 65 Am under a magnetic field of (1000 / 4π (kA / m) 2 / kg) For each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was rapidly mixed and stirred in a container at over 100°C to treat the respective fine particles.

[0166] • Phenolic: 10% by mass Formaldehyde solution: 6% by mass (40% formaldehyde by mass, 10% methanol by mass, 50% water by mass) • Magnetite treated with the above silane compound 1:58 mass% • Magnetite treated with the above silane compound: 2:26% by mass The above materials, along with 5 parts of a 28% by mass aqueous ammonia solution and 20 parts of water, were placed in a flask. The mixture was stirred and heated to 85°C for 30 minutes, and the temperature was maintained there. Polymerization was carried out for 3 hours to cure the resulting phenolic resin. The cured phenolic resin was then cooled to 30°C, water was added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Next, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60°C to obtain spherical carrier 1 with magnetic material dispersion. The volume-based 50% particle size (D50) was 34.2 μm.

[0167] <Example of manufacturing a two-component developer 1> 92.0 parts of carrier 1 and 8.0 parts of toner 1 were added and mixed using a V-type mixer (V-20, manufactured by Seishin Corporation) to obtain a two-component developer 1.

[0168] <Manufacturing examples of two-component developers 2-38> In the example of manufacturing two-component developer 1, the manufacturing process was carried out in the same manner except that the toner was changed as shown in Table 3, and two-component developers 2 to 38 were obtained. [Table 3]

[0169] <Toner Evaluation Method> (1) Measurement of image density changes A Canon imagePress C800 full-color copier was used as the image forming apparatus. The above two-component developer was placed in the cyan developer unit of the image forming apparatus, and the above toner was placed in the cyan toner container, and the evaluation described below was performed. The modification was the removal of the mechanism that discharges excess magnetic carriers from inside the developer unit. The evaluation paper was plain paper GF-C. 081(A4, basis weight 81.4g / m 2 (Sold by Canon Marketing Japan Inc.)

[0170] The amount of toner transferred to the paper in an FFh image (solid color image) is 0.45 mg / cm². 2 The settings were adjusted accordingly. FFh is a value representing 256 gradations in hexadecimal, where 00h is the first gradation of 256 gradations (white area) and FF is the 256th gradation of 256 gradations (solid area). First, a test was conducted on 7,000 images with an image ratio of 1%. During the continuous feeding of 7,000 sheets, the same development and transfer conditions (no calibration) as the first sheet were used.

[0171] Subsequently, a test was conducted to print 7,000 images at an image ratio of 80%. During the continuous feeding of 7,000 sheets, the same development and transfer conditions (without calibration) as the first sheet were used. After printing at an image ratio of 1%, the image density of the first sheet printed at an image ratio of 80% was used as the initial density, and the density of the 7,000th image printed at an image ratio of 80% was measured and evaluated.

[0172] The above tests were conducted under normal temperature and humidity conditions (N / N; temperature 25°C, relative humidity 55%) and high temperature and high humidity conditions (H / H; temperature 30°C, relative humidity 80%). An X-Rite color reflectance densitometer (500 series: manufactured by X-Rite) was used to measure the density of the 7,000th image printed at an image ratio of 80% compared to the initial density, and the difference Δ was used to rank the images according to the following criteria. A rating of D or higher was considered good. (Evaluation criterion: Image density difference Δ) A: Less than 0.02 B: 0.02 or higher, less than 0.05 C: 0.05 or higher, less than 0.10 D: 0.10 or more and less than 0.15 E: 0.15 or more

[0173] (2) Method for Evaluating Fog on Non-Image Areas (White Background Areas) After Durability Testing As an image forming apparatus, a modified full-color copier imagePress C800 manufactured by Canon was used. Two-component developer 1 was charged into the developing unit of the cyan station, and evaluation was performed. The toner deposition amount on paper in an FFh image (solid image) was 0.45 mg / cm 2 Adjustments were made to achieve the above condition. The evaluation environments were N / N and H / H environments, and the evaluation paper was plain copier paper GFC-081 (A4, basis weight 81.4 g / m 2 sold by Canon Marketing Japan Inc.) was used. In each environment, after outputting 70,000 sheets of a 1 cm×1 cm FFh image at the center of A4 paper, fog on the white background area was measured.

[0174] The reflectance Dr (%) of the evaluation paper before image formation was measured using a reflectometer ("REFLECTOMETER MODEL TC-6DS" manufactured by Tokyo Denshoku Co., Ltd.). The reflectance Ds (%) of the 00H image area (white background area) after durability testing (on the 70001st sheet) was measured. From the obtained Dr and Ds, fog (%) was calculated using the following formula. Fog (%) = Dr(%) - Ds(%) The evaluation results were ranked according to the following criteria. Grades D or higher were judged as good. (Evaluation Criteria Fog (%)) A: Less than 1.0% B: 1.0% or more and less than 1.5% C: 1.5% or more and less than 2.0% D: 2.0% or more and less than 2.5% E: 2.5% or more

[0175] (3) Method for Evaluating Charge Stability The amount of triboelectric charge on toner was calculated by collecting toner on an electrostatic latent image carrier using a metal cylindrical tube and a cylindrical filter. Specifically, the amount of triboelectric charge on the toner on the electrostatic latent image carrier was measured using a Faraday cage. A Faraday cage is a coaxial double cylinder with the inner and outer cylinders insulated. If a charged object with charge Q is placed inside the inner cylinder, electrostatic induction makes it as if a metal cylinder with charge Q were present. This induced charge was measured using an electrometer (Kessley 6517A, manufactured by Kessley), and the amount of charge Q (mC) divided by the toner mass M (kg) in the inner cylinder (Q / M) was defined as the amount of triboelectric charge on the toner. The amount of triboelectric charge on toner (mC / kg) = Q / M Evaluation image: A 2cm x 5cm image of FFh is placed in the center of an A4 sheet of paper.

[0176] First, the evaluation image described above was formed on the electrostatic latent image carrier. Before it was transferred to the intermediate transfer medium, the rotation of the electrostatic latent image carrier was stopped, and the toner on the electrostatic latent image carrier was collected by suction using a metal cylindrical tube and a cylindrical filter, and the [initial Q / M] was measured. Subsequently, the developer was left inside the evaluation machine in an H / H environment for 4 weeks, and then the same procedure as before was performed to measure the amount of charge per unit mass Q / M (mC / kg) on ​​the electrostatic latent image carrier after the period of time. From the initial Q / M per unit mass on the electrostatic latent image carrier and the Q / M per unit mass on the electrostatic latent image carrier after the period of time, the rate of change of Q / M after the period of time ([initial Q / M] - [Q / M after being left in an H / H environment]) × 100 / [initial Q / M] was calculated and judged according to the following criteria. A score of D or higher was judged to be good. (Evaluation Criteria) A: Rate of change is less than 2% B: Change rate is between 2% and less than 5% C: Change rate is 5% or more but less than 10% D: Rate of change is between 10% and less than 15% E: Change rate of 15% or more

[0177] <Evaluation results for Examples 1-32> The evaluation results for Examples 1 to 32 are shown in Table 4. Examples 18-32 below are considered reference examples 18-32. <Evaluation results for Comparative Examples 1-6> The evaluation results for Comparative Examples 1-6 are shown in Table 4.

[0178] [Table 4]

[0179] This disclosure relates to the following configuration. (Composition 1) Fine particles of silicon polymer, The fine particles have pores, The total pore volume of the fine particles is 0.35 cm³. 3 / g~1.00cm 3 / g The number-average particle size of the primary particles of the fine particles is 0.05 μm to 0.30 μm. The silicon polymer has siloxane bonds and Si-R 1 Having a bond, The R 1 This represents an alkyl group with 1 to 6 carbon atoms. The fine particles 29 In the chart obtained by Si-NMR measurement, the total peak area corresponding to the silicon polymer is denoted as A, and the Si-R 1 When the corresponding peak area is denoted as B, A and B are given by the following formula (1) 10.0 ≤ B / A × 100 ≤ 45.0 ···(1) Fine particles characterized by satisfying the following conditions. (Configuration 2) The fine particles according to configuration 1, wherein the volume average diameter of the pores in the fine particles is 7 nm to 20 nm. (Composition 3) The theoretical BET specific surface area of ​​the aforementioned fine particles is X(m²). 2 Let Y(m²) be the BET specific surface area of ​​the fine particles measured by the BET multipoint method, and let Y(m²) be the BET specific surface area of ​​the fine particles measured by the BET multipoint method. 2 When we set it to / g, The fine particles according to configuration 1 or 2, wherein X and Y satisfy the following formula (2). 3.0 ≤ Y / X ≤ 8.0 ···(2) (Composition 4) The aforementioned fine particles29 In a chart obtained by Si-NMR measurement, when the total peak area corresponding to the silicon polymer is denoted as SA, the peak area corresponding to the Q unit structure as S4, the peak area corresponding to the T unit structure as S3, and the peak area corresponding to the D unit structure as S2, the fine particles according to any of configurations 1 to 3 satisfy the following formulas (I) to (III). 0.20 ≤ S4 / SA ≤ 0.60 ···(I) 0 ≤ S3 / SA ≤ 0.50 ···(II) 0.20≦S2 / SA≦0.70 (III) (Composition 5) The fine particles according to any one of configurations 1 to 4, wherein the Young's modulus of the fine particles is 1500 MPa to 30000 MPa. (Composition 6) In the X-ray photoelectron spectroscopy measurement of the surface of the aforementioned fine particles, when the elemental concentration of silicon is dSi, the elemental concentration of oxygen is dO, the elemental concentration of carbon is dC, and the total is 100.0 atomic%, The fine particles according to any one of configurations 1 to 5, wherein the dC is 10.0 atomic% to 50.0 atomic%. (Composition 7) The fine particles according to any one of configurations 1 to 6, wherein the fine particles are surface-treated with at least one compound selected from the group consisting of alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, fluoroalkylsilane compounds, and siloxane compounds. (Configuration 8) The fine particles according to any one of configurations 1 to 7, wherein the average circularity of the fine particles is 0.85 to 0.95. (Composition 9) The fine particles according to any one of configurations 1 to 8, wherein the degree of hydrophobicity of the fine particles determined by methanol titration is 50% to 60% by volume. (Composition 10) The fine particles according to any one of configurations 1 to 9, wherein the silicon polymer is a condensed polymer of at least one silicon compound selected from the group consisting of silicon compounds having a structure represented by the following formula (A). TIFF0007919941000007.tif38170(In formula (A), R 12 , R 13 , R 14 and R 15 Each of these independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a reactive group, and the reactive group represents a halogen atom, a hydroxyl group, an acetoxy group, or an alkoxy group having 1 to 6 carbon atoms. 12 , R 13 , R 14 and R 15 At least one of them is the reactive group. (Composition 11) An external additive for toner containing fine particles as described in any of the components 1 to 10. (Composition 12) A toner having toner particles and an external additive for toner, The toner particles contain a binder resin, A toner in which the toner additive is the toner additive described in configuration 11. (Composition 13) The toner according to configuration 12, wherein the content of the toner additive in the toner is 0.1 parts by mass to 20.0 parts by mass per 100 parts by mass of the toner particles.

Claims

1. A silicon polymer fine particle obtained by hydrolysis and condensation reaction of a silane mixture comprising a tetraalkoxysilane and at least one silane selected from the group consisting of a tetraalkoxysilane and a dialkoxysilane in which two methyl groups are bonded to silicon, The fine particles are surface-treated with at least one compound selected from the group consisting of alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, fluoroalkylsilane compounds, and siloxane compounds. The fine particles have pores, The total pore volume of the fine particles is 0.35 cm³. ３ / g to 1.00cm ３ / g, The number-average particle size of the primary particles of the fine particles is 0.05 μm to 0.30 μm. The silicon polymer has siloxane bonds and Si-R １ Having a bond, The R １ This represents an alkyl group having 1 to 6 carbon atoms. The fine particles ２９ In the chart obtained by Si-NMR measurement, the total peak area corresponding to the silicon polymer is denoted as A, and the Si-R １ When the corresponding peak area is denoted as B, A and B are given by the following formula (1) 10.0 ≤ B / A × 100 ≤ 45.0 ... (1) Satisfying the conditions, Fine particles used in toner additives, characterized in that the volume-average diameter of the pores of the fine particles is 7 nm to 20 nm.

2. The theoretical BET specific surface area of ​​the aforementioned fine particles is X (m ２ Let Y(m²) be the BET specific surface area of ​​the fine particles measured by the BET multipoint method, where Y(m²) is the BET specific surface area measured by the BET multipoint method. ２ When / g) The fine particles according to claim 1, wherein X and Y satisfy the following formula (2). 3.0≦Y / X≦8.0...(2)

3. The fine particles described above ２９ In a chart obtained by Si-NMR measurement, when the total peak area corresponding to the silicon polymer is defined as SA, the peak area corresponding to the Q unit structure is defined as S4, the peak area corresponding to the T unit structure is defined as S3, and the peak area corresponding to the D unit structure is defined as S2, the SA, S4, S3 and S2 satisfy the following formulas (I) to (III). The fine particles according to claim 1 or 2, wherein 0.20≦S4 / SA≦0.60...(I) 0≦S3 / SA≦0.50...(II) 0.20≦S2 / SA≦0.70...(III)

4. The fine particles according to claim 1 or 2, wherein the Young's modulus of the fine particles is 1,500 MPa to 30,000 MPa.

5. In the X-ray photoelectron spectroscopy measurement of the surface of the aforementioned fine particles, when the elemental concentration of silicon is dSi, the elemental concentration of oxygen is dO, the elemental concentration of carbon is dC, and the total is 100.0 atomic%, The fine particles according to claim 1 or 2, wherein the dC is 10.0 atomic% to 50.0 atomic%.

6. The fine particles according to claim 1 or 2, wherein the average circularity of the fine particles is 0.85 to 0.

95.

7. The fine particles according to claim 1 or 2, wherein the degree of hydrophobicity of the fine particles determined by methanol titration is 50% by volume to 60% by volume.

8. The fine particles according to claim 1 or 2, in a silane mixture comprising a tetraalkoxysilane and at least one silane selected from the group consisting of a dialkoxysilane having two methyl groups bonded to silicon, wherein the proportion of at least one silane selected from the group consisting of a dialkoxysilane having two methyl groups bonded to silicon is 40 mol% to 75 mol%.

9. An external additive for toner containing the fine particles described in claim 1 or 2.

10. A toner having toner particles and an external additive for toner, The toner particles contain a binder resin, The toner is an external additive for toner as described in claim 9.

11. The toner according to claim 10, wherein the amount of the toner additive in the toner is 0.1 to 20.0 parts by mass per 100 parts by mass of the toner particles.

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