Toner additives and toner

Abstract

To provide a toner external additive which improves scratch resistance, and heat and pressure resistance while minimizing durability deterioration due to contamination.SOLUTION: A toner external additive disclosed herein consists of organosilicon polymer particles with fine pores, containing a compound A having a melting point in a range of 70 to 120°C, inclusive, and a surface free energy of 45 mJ / m2 or less.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, there has been a demand for improving the quality of image output products (erasability, heat and pressure resistance), including POD machines (on-demand printers). Conventionally, in order to improve erasability and heat and pressure resistance, a means of containing a large amount of wax in the toner matrix for the purpose of reducing the friction coefficient of the fixed image has been common (Patent Document 1). In addition, a method of externally adding fine particles whose surface is coated with wax to the toner (Patent Document 2) and a method of externally adding fine particles containing wax to the toner are also known (Patent Documents 3 and 4).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] When a large amount of wax is contained in the toner matrix as in Patent Document 1, wax is exposed on the toner surface, and there is a problem that the durability deteriorates due to contamination of the carrier and members. The same applies when the surface of the external additive is coated with wax as in Patent Document 2. In addition, in Patent Documents 3 and 4, wax is encapsulated in resin fine particles. However, since the resin fine particles are soft, there has been a problem that the resin fine particles are crushed by stress in the developing machine and the wax is exposed, resulting in deterioration of durability as well. An object of the present invention is to provide an external additive for toner and a toner that solve the above problems. Specifically, it is to provide an external additive for toner and a toner that can improve rubbing resistance and heat and pressure resistance while suppressing deterioration of durability due to contamination.

Means for Solving the Problems

[0005] The present invention is an organosilicon polymer particle having pores, the organosilicon polymer particle contains a compound A having a melting point of 70°C or higher and 120°C or lower, the surface free energy of the compound A is 45 mJ / m 2 or less, and it is an external additive for toner characterized by this. Further, the present invention is a toner having toner particles and an external additive for toner, the external additive for toner is an external additive for toner having the above configuration, and it is a toner characterized by this.

Effects of the Invention

[0006] When the external additive for toner of the present invention is used, rubbing resistance and heat and pressure resistance can be improved without impairing durability.

Brief Description of the Drawings

[0007] [Figure 1] 4]It is an explanatory diagram of a heat treatment apparatus used for manufacturing the toner of the present invention.

Embodiments for Carrying Out the Invention

[0008] In the present invention, the description of "○○ or more and ×× or less" or "○○ to ××" representing a numerical range means a numerical range including the lower limit and the upper limit which are endpoints, unless otherwise specified.

[0009] The inventors believe the mechanism by which the effects of the present invention are realized is as follows.

[0010] Traditionally, silica particles used as external additives for toners have very few pores inside, so when wax treatment is applied, most of the wax is introduced to the particle surface. To improve abrasion resistance, heat resistance, and pressure resistance, a small amount of wax is insufficient, requiring a large amount of wax. However, this results in the particle surface being covered with a large amount of wax, contaminating the carrier and components and worsening durability.

[0011] On the other hand, if an organosilicon polymer with pores is used, wax can be introduced into the pores, allowing for the introduction of a large amount of wax while suppressing the exposure of wax to the surface. Furthermore, it is believed that the wax in the pores will seep out onto the image surface in response to the heat and pressure during fixing, thereby reducing the coefficient of friction on the image surface and improving abrasion resistance, heat resistance, and pressure resistance without compromising durability, leading to the present invention.

[0012] [External additives for toner] The toner additive of the present invention is an organosilicon polymer particle having pores, The organosilicon polymer particles contain compound A, which has a melting point of 70°C or higher and 120°C or lower. The surface free energy of compound A is 45 mJ / m 2 The following characteristics apply:

[0013] The toner additive of the present invention is an organosilicon polymer having pores. Having pores allows compound A to be introduced into the additive. Furthermore, because it is an organosilicon polymer, it has better affinity with compound A than inorganic compounds such as silica, allowing compound A to be supported within the polymer.

[0014] <Silicon polymer particles> 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.

[0015] 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 added to the spherical silicon polymer particle dispersion to obtain hydrophobic spherical silicon polymer particles.

[0016] 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.

[0017] 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 It is selected within the range of parts by mass or more and 1 part by mass or less.

[0018] Catalyst usage amount 1 × 10 -3If the amount of catalyst is 1 part by mass or more, the reaction will proceed sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the silicon polymer particles will be low, making hydrolysis easier. The amount of water used is preferably 2 moles to 15 moles per mole of silicon compound. If the amount of water is 2 moles or more, the hydrolysis reaction will proceed sufficiently, and if it is 15 moles or less, productivity will be improved.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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 parts by mass to 12.5 parts by mass per 100 parts by mass of the mixture of water and organic solvent.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] Furthermore, in order to create porous particles like those in this case, it is preferable to proceed to the next third step while the polycondensation is still in an incomplete state before it has completely progressed.

[0027] 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.

[0028] 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 used, but filtration is preferred because it is easy to operate. The filtration method is not particularly limited, and any known apparatus such as vacuum filtration, centrifugal filtration, or pressure filtration may be selected. The filter paper, filter, filter cloth, etc. used for filtration are not particularly limited as long as they are industrially available, and can be appropriately selected according to the apparatus used.

[0029] The silicon polymer particles may be surface-treated using known methods such as silane coupling agents or silicone oils. Surface treatment is preferable because it makes it easier to support compound A introduced into the particles.

[0030] The monomer used can be appropriately selected depending on its compatibility with the solvent and catalyst, or its hydrolyzability, but examples of tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanatesilane, with tetraethoxysilane being preferred.

[0031] Trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxy Examples include xysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0032] Examples of bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and dimethyldimethoxysilane, with dimethyldimethoxysilane being preferred.

[0033] 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.

[0034] <Compound A> The toner additive of the present invention contains compound A, and its melting point is between 70°C and 120°C. When the melting point of compound A is below 70°C, compound A present on the image surface after fixing softens when exposed to high temperatures, resulting in no heat resistance or pressure resistance effect. When the melting point of compound A is higher than 120°C, compound A does not sufficiently seep out from the additive even when heat and pressure are applied during fixing, resulting in no effect on abrasion resistance or heat resistance and pressure resistance. The preferred range for the melting point is between 70°C and 100°C, and more preferably between 70°C and 90°C.

[0035] The toner additive of the present invention contains compound A, and its surface free energy is 45 mJ / m². 2 The following is true: The surface free energy of compound A is 45 mJ / m². 2 When the value is greater than this, covering the image surface with compound A does not reduce the coefficient of friction, and therefore has no effect on abrasion resistance or heat and pressure resistance. The preferred range for the surface free energy is 40 mJ / m 2 The following is more preferable: 35 mJ / m 2 The following applies:

[0036] The compound A is preferably a hydrocarbon compound or an ester compound. Examples of hydrocarbon compounds include hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, while examples of ester compounds include waxes mainly composed of fatty acid esters, such as carnauba wax. When a toner additive is treated with such a compound, it can be supported in the pores due to its good affinity with the toner additive, thereby suppressing deterioration of durability due to contamination.

[0037] The penetration degree of compound A at 25°C is preferably 10 or less. When the penetration degree of compound A is within the above range, the surface becomes stronger when the image surface is covered with compound A after fixing, thus improving abrasion resistance. From the above viewpoint, it is more preferable that the penetration degree of compound A at 25°C is 6 or less.

[0038] The content of compound A is preferably 5.0 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of organosilicon polymer particles. When the content of compound A is within the above range, compound A can be introduced only into the pores without being exposed on the surface of the toner additive, and a sufficient amount seeps out onto the image surface when heat and pressure are applied during fixing, which is effective in improving abrasion resistance and heat and pressure resistance. From the above viewpoint, the content of compound A is more preferably 8.0 parts by mass or more and 15.0 parts by mass or less.

[0039] In the present invention, the number-average particle size of the primary particles of the toner additive is preferably 0.05 μm or more and 0.30 μm or less. When the number-average particle size is within the above range, the additive adheres to the toner, and compound A is easily released when heat and pressure are applied during the fixing process, which is effective in improving abrasion resistance and heat and pressure resistance. From the above viewpoint, a number-average particle size of 0.08 μm or more and 0.15 μm or less is more preferable.

[0040] The average particle size of the external additive for toner can be controlled by hydrolysis and condensation conditions (reaction temperature, reaction time, stirring time), pH, and type of catalyst during the reaction in a wet manufacturing method. For example, to increase the average particle size, methods such as lowering the temperature during the hydrolysis reaction, shortening the stirring time, lowering the pH of the solution, and increasing the pH of the solution during condensation can be mentioned. To decrease the average particle size, methods such as increasing the temperature during the hydrolysis reaction, lengthening the stirring time, increasing the pH of the solution, and lowering the pH of the solution during condensation can be mentioned.

[0041] When the BET specific surface area of the external additive for toner in the present invention is X (m 2 / g), and the BET specific surface area of the external additive for toner after washing with hexane is Y (m 2 / g), X and Y preferably satisfy 2.0 ≦ Y / X When the pore part is filled with compound A by treating the external additive with compound A, the value of the BET specific surface area changes compared to before the treatment. Therefore, the degree of change in this BET specific surface area can be used as an index of how much the pore part is filled with compound A. Since compound A and the external additive are not chemically bonded, the value of the BET specific surface area (Y) before treatment can be obtained by washing the external additive after treatment with compound A with hexane to remove compound A. When Y / X is within the above range, the pores are filled with compound A, so it is effective for abrasion resistance and heat and pressure resistance. It is more preferable that 3.0 ≦ Y / X from the above viewpoint.

[0042] Also, when the theoretical BET specific surface area calculated from the particle size of the external additive for toner after washing is Z (m 2 / g), Y and Z preferably satisfy [[ID=​​​​​Y / X can be controlled by changing the Y / Z ratio and the processing conditions for compound A. First, in the wet manufacturing method, Y / Z can be controlled by the hydrolysis and condensation conditions during the reaction (reaction temperature, reaction time, stirring time), pH, type of catalyst, and ratio of added monomers. For example, to increase Y / Z, methods include increasing the mixing ratio of bifunctional silane, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the pH of the solution, and lowering the temperature during hydrolysis. To decrease Y / Z, methods include increasing the mixing ratio of 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.

[0044] To increase the Y / X ratio, methods include increasing the Y / Z ratio and then increasing the processing volume of compound A, lengthening the processing time, or raising the processing temperature. To decrease the Y / X ratio, methods include decreasing the Y / Z ratio and then reducing the processing volume of oil, shortening the processing time, or lowering the processing temperature.

[0045] The total pore volume of the pores in the aforementioned external additive for toner after washing is 0.30 cm³. 3 / g or more 1.00cm 3 It is preferable that the amount is less than or equal to / g. Specifically, this refers to the total pore volume of fine particles measured by the BJH method in the range of pore diameter of 1.7 nm to 300.0 nm. When the total pore volume is within the above range, an effective amount of compound A for separation can be introduced into the pores. The total pore volume is 0.35 cm³. 3 / g or more 0.60cm 3 From the above perspective, it is more preferable that the value be less than or equal to / g.

[0046] The total pore volume of toner additives can be controlled in wet manufacturing methods by the hydrolysis and condensation conditions during the reaction (reaction temperature, reaction time, stirring time), pH, type of catalyst, and ratio of added monomers. For example, to increase the 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. To decrease the 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.

[0047] The volume-average diameter of the pores in the external additive for toner after washing is preferably 5 nm or more and 20 nm or less. When the average diameter of the pores is within the above range, even compounds with a certain degree of viscosity can be introduced into the pores, and furthermore, when pressure is applied during the fixing process, the compounds in the pores tend to seep to the surface, thus providing a separation effect. From the above viewpoint, it is more preferable that the volume-average diameter of the pores is 8 nm or more and 5 nm or less.

[0048] The average pore size of toner additives can be controlled in wet manufacturing methods by the hydrolysis and condensation conditions during the reaction (reaction temperature, reaction time, stirring time), pH, type of catalyst, and ratio of added monomers. For example, to increase the pore size, 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. To decrease the pore size, 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.

[0049] The detailed method for measuring the relative abundances of the constituent components of organosilicon polymer particles will be described later, 29In 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 organosilicon polymer particles. The structure bonded to Si can be identified by specifying the position of each peak using a standard sample. 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 (Chemical Formula 1), D unit structure (Chemical Formula 2), T unit structure (Chemical Formula 3), and Q unit structure (Chemical Formula 4) to the total peak area can be calculated.

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka] (Ra, Rb, Rc, Rd, Re, and Rf each represent alkyl groups with 1 to 6 carbon atoms.)

[0054] The toner additive of the present invention is 29 In the chart obtained by Si-NMR measurement, when the total peak area originating from the silicon polymer is denoted as SA and the peak area originating from the D unit is denoted as S2, it is preferable that 0.20 ≤ S2 / SA ≤ 0.70 is satisfied. Within this range, the pore diameter and pore volume are optimized, improving abrasion resistance and heat and pressure resistance without compromising durability. From the above viewpoint, it is more preferable that 0.50 ≤ S2 / SA ≤ 0.70 is satisfied.

[0055] The toner additive of the present invention is 29In the chart obtained by Si-NMR measurement, when the total peak area originating from the silicon polymer is denoted as SA, the peak area originating from Q units as S4, and the peak area originating from T units as S3, 0.20 ≤ S4 / SA ≤ 0.60, 0.00 ≤ S3 / SA ≤ 0.50 It is preferable that the following relationship is satisfied. When the values ​​are within the above range, the pore diameter and pore volume are optimized, improving abrasion resistance and heat and pressure resistance without compromising durability. From the above viewpoint, it is more preferable that 0.30 ≤ S4 / SA ≤ 0.50 and 0.00 ≤ S3 / SA ≤ 0.20.

[0056] In the present invention, the toner additive preferably has a compression cohesiveness value of 20 mJ or more and 70 mJ or less at 25°C and 30 kPa, and a compression cohesiveness value of 120 mJ or more and 180 mJ or less at 100°C and 60 kPa. Compression cohesiveness represents the degree of cohesiveness of particles after they have been compressed under a predetermined pressure. When compound A is introduced into the pores, it is thought that the degree of cohesiveness increases as more heat and pressure are applied, as more compound A seeps out. When the compression cohesiveness value at 25°C and 30 kPa is within the above range, compound A does not seep out when no high pressure is applied and remains supported in the pores, so it does not impair developability due to contamination. When the compression cohesiveness value at 100°C and 60 kPa is within the above range, compound A seeps out when pressure is applied, which is effective in improving abrasion resistance and heat and pressure resistance. From the above viewpoint, it is more preferable that the degree of compression cohesion at 25°C and 30kPa is 30mJ or more and 60mJ or less, and that the degree of compression cohesion at 100°C and 60kPa is 140mJ or more and 170mJ or less.

[0057] The degree of compression aggregation of the toner additive can be controlled by the pore volume, pore diameter, and the processing amount of compound A. The methods for controlling the pore volume and pore diameter are as described above.

[0058] The content of the toner additive of the present invention relative to toner particles (toner matrix particles) is preferably 0.1 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of toner particles. Within this range, a sufficient amount of compound A seeps onto the image surface during fixing, providing effects on abrasion resistance and heat and pressure resistance. From the above viewpoint, a content of 0.5 parts by mass or more and 15.0 parts by mass or less is more preferable. Even more preferable is 1.0 part by mass or more and 10.0 parts by mass or less.

[0059] The adhesion rate of the toner additive of the present invention to the toner matrix particles is preferably 50% or more, and more preferably 70% or more, based on the mass of the toner. When the adhesion rate is within the above range, a sufficient amount of the toner additive is present on the transferred image during fixing, thus providing effects on abrasion resistance and heat and pressure resistance. The adhesion rate of the toner additive to the toner matrix particles can be controlled by the toner manufacturing method. For example, one method is to heat-treat the toner after mixing the toner additive with the toner particles (details of the heat treatment method will be described later).

[0060] [Toner particles] Next, the composition of toner particles to which the toner additive of the present invention is added will be described.

[0061] <Binding resin> The binder resin used in the toner of the present invention is not particularly limited, and the following polymers or resins can be used.

[0062] For example, monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-α-chloromethacrylate methyl copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers can be used. Among these, polyester resins are preferred from the viewpoint of durability and electrostatic stability. Furthermore, it is preferable from the viewpoint of environmental stability and electrostatic stability that the acid value of the polyester resin is 0.5 mg KOH / g or more and 40 mg KOH / g or less. The acid value in the polyester resin interacts with the Si-CH3 in the external additive, which can further improve the toner's electrostatic properties in a high-humidity environment. More preferably, it is 1 mg KOH / g or more and 20 mg KOH / g or less, and even more preferably 1 mg KOH / g or more and 15 mg KOH / g or less.

[0063] <Coloring agent> The toner of the present invention may contain a coloring agent as needed. Examples of coloring agents include the following:

[0064] Examples of black colorants include carbon black and black colorants prepared by mixing yellow, magenta, and cyan colorants. While pigments may be used alone as colorants, using dyes and pigments in combination is preferable from the standpoint of full-color image quality to improve clarity.

[0065] 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.

[0066] 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.

[0067] 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 phthalimidomethyl groups are substituted onto the phthalocyanine skeleton.

[0068] CI Solvent Blue 70 is a dye used for cyan toner.

[0069] The following pigments are used for yellow toner: 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.

[0070] CI Solvent Yellow 162 is a dye used for yellow toner.

[0071] The coloring agent content is preferably 0.1 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the binder resin.

[0072] <wax> The toner of the present invention may contain wax as needed. Examples of waxes include the following:

[0073] Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax; and deoxidized fatty acid esters such as deoxidized carnauba wax, which have been partially or completely deoxidized.

[0074] Furthermore, the following can be listed: saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearate amide, ethylenebiscaprate amide, ethylenebislaurate amide, and hexamethylene Saturated fatty acid bisamides such as bis-stearamide; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'dioleyladipamide, and N,N'dioleylsebacamide; aromatic bisamides such as m-xylenebis-stearamide and N,N'distearylisophthalamide; aliphatic metal salts (commonly known as 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; and methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils.

[0075] The wax content is preferably 2.0 parts by mass or more and 30.0 parts by mass or less per 100 parts by mass of the binder resin.

[0076] <Charge control agent> The toner of the present invention may optionally contain a charge control agent. While known charge control agents can be used in the toner, metal compounds of aromatic carboxylic acids that are colorless, have a fast charging speed for the toner, and can stably maintain a constant charge are particularly preferred.

[0077] 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 or sulfonic acid ester as a side chain, polymer compounds having carboxylate salt or carboxylic acid ester as a side chain, boron compounds, urea compounds, silicon compounds, and calixarenes. The charge control agent may be added internally or externally to the toner particles.

[0078] The amount of charge control agent added is preferably 0.2 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the binder resin.

[0079] <Inorganic fine powder> In addition to the toner additives described above, the toner of the present invention may also contain other inorganic fine powders as needed. The inorganic fine powder may be added internally to the toner particles or mixed with the toner mother particles as an external additive. As the external additive, an inorganic fine powder such as silica is preferred. The inorganic fine powder is preferably hydrophobized with a hydrophobic agent such as a silane compound, silicone oil, or a mixture thereof.

[0080] As an external additive for improving fluidity, it has a specific surface area of ​​50 m². 2 / g or more 400m 2 Inorganic fine powder with a specific surface area of ​​less than / g is 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. The above inorganic fine powder is preferably used in amounts of 0.1 parts by mass to 10.0 parts by mass per 100 parts by mass of toner particles. When the above range is met, the effect of static charge stability is easily obtained.

[0081] <Developer> The toner of the present invention can be used as a one-component developer, but to further improve dot reproduction, it is preferable to mix it with a magnetic carrier and use it as a two-component developer, as this allows for stable images over a long period of time. That is, a two-component developer containing toner and a magnetic carrier is preferable, wherein the toner is the toner of the present invention.

[0082] As magnetic carriers, generally known materials can be used, such as iron powder with an oxidized surface, or iron powder without oxidation, or magnetic materials such as metal particles like iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, or their alloy particles, oxide particles, or ferrite, or 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.

[0083] When toner is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio is preferably 2% to 15% by mass, and more preferably 4% to 13% by mass, as the toner concentration in the two-component developer, which usually yields good results.

[0084] <Method for manufacturing toner particles and method for manufacturing toner> There are no particular limitations on the method for producing toner particles, and conventionally known manufacturing methods such as suspension polymerization, emulsification and agglomeration, melt kneading, and dissolution and suspension can be employed.

[0085] Toner can be obtained by mixing the toner additive of the present invention and, if necessary, other external additives with the obtained toner particles. Mixing of the toner particles with the toner additive of the present invention and other 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).

[0086] Furthermore, in order to control the adhesion rate of the toner additive to the toner particles, it is preferable to mix the toner additive with the toner particles to obtain a toner particle mixture and then perform heat treatment. For example, heat treatment can be performed using hot air with the heat treatment apparatus shown in Figure 1.

[0087] The heat treatment apparatus comprises a treatment chamber 6 for heat-treating a toner particle mixture, a toner particle mixture supply means for supplying the toner particle mixture to the treatment chamber 6, a hot air supply means 7 for supplying hot air for heat-treating the toner particle mixture supplied from the toner particle mixture supply means, and a recovery means 10 for discharging and recovering the heat-treated toner particles from an outlet provided in the treatment chamber 6.

[0088] The heat treatment apparatus shown in Figure 1 further includes a regulating means 9 as a cylindrical member, and the processing chamber 6 has a cylindrical shape that covers the outer surface of the regulating means 9. The hot air supply means 7 is provided on one end of the cylindrical shape of the processing chamber 6 so that the hot air flows through the cylindrical processing chamber 6 in a rotating manner. The toner particle mixture supply means consists of a plurality of supply pipes 5 provided on the outer circumference of the processing chamber 6.

[0089] Furthermore, the discharge port provided in the processing chamber 6 is located on the outer circumference of the end of the processing chamber 6 opposite to the side where the hot air supply means 7 is provided, so as to be on the extension of the rotational direction of the toner particle mixture. A heat treatment using a heat treatment apparatus having the above configuration will be described below.

[0090] The toner particle mixture supplied in a fixed quantity by the raw material quantitative supply means 1 is guided by compressed gas adjusted by the compressed gas flow rate adjustment means 2 into an introduction pipe 3 installed vertically on the raw material quantitative supply means 1. The mixture that has passed through the introduction pipe is uniformly dispersed by a conical projection member 4 provided in the center of the raw material quantitative supply means 1 and guided into eight radially spreading supply pipes 5 and then into a processing chamber 6 where heat treatment is performed.

[0091] At this time, the flow of the mixture supplied to the processing chamber 6 is restricted by a restricting means 9 provided within the processing chamber 6 to regulate the flow of the mixture. As a result, the mixture supplied to the processing chamber is heat-treated while swirling within the processing chamber 6, and then cooled.

[0092] The heat for heat-treating the supplied mixture is supplied from the hot air supply means 7, distributed by the distribution member 12, and introduced into the processing chamber 6 in a spiral motion by the swirling member 13 for swirling the hot air. The swirling member 13 for swirling the hot air has multiple blades, and the swirling of the hot air can be controlled by the number and angle of these blades. The hot air is supplied from the outlet 11 of the hot air supply means.

[0093] The heat-treated toner particles are cooled by the cold air supplied from the cold air supply means 8 (cold air supply means 8-1, 8-2, and 8-3).

[0094] Next, the cooled toner particles are collected as toner by a collection means 10 located at the lower end of the processing chamber. A blower (not shown) is provided at the end of the collection means, and the particles are transported by suction.

[0095] Furthermore, the powder particle supply port 14 is positioned so that the swirling direction of the supplied mixture and the swirling direction of the hot air are in the same direction, and the recovery means 10 of the hot sphere shaping apparatus is provided on the outer periphery of the processing chamber to maintain the swirling direction of the swirled powder particles. In addition, the cold air supplied from the cold air supply means 8 is configured to be supplied horizontally and tangentially from the outer periphery of the apparatus to the circumferential surface of the processing chamber.

[0096] <Image forming apparatus> When using the toner of the present invention, an image forming apparatus is used that includes a support, an electrophotographic photoreceptor having a photosensitive layer formed on the support, an image forming means for forming an electrostatic image on the electrophotographic photoreceptor, a developing means for supplying toner to the electrostatic image formed on the electrophotographic photoreceptor, a transfer means for transferring the toner image from the electrophotographic photoreceptor to a recording medium, and a fixing means for fixing the toner image transferred to the recording medium to the recording medium with heat and pressure.

[0097] [Methods for measuring various physical properties] The following describes methods for measuring various physical properties.

[0098] <Separation of toner additives and toner particles from toner> The physical properties of toner can also be measured using toner additives separated from the toner 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.

[0099] The centrifugation tube is shaken in the shaker described above at a rate of 350 strokes per minute for 20 minutes. After shaking, the solution is transferred to a 50 mL glass tube for a swing rotor and centrifuged in a centrifuge at 3500 rpm for 30 minutes. After centrifugation, the toner is present in the uppermost layer of the glass tube, and the toner additive is present in the lower aqueous solution layer. The lower aqueous solution is collected and centrifuged to separate the sucrose from the toner additive, and the toner additive is collected. If necessary, centrifugation is repeated to ensure sufficient separation, then the dispersion is dried and the toner additive is collected.

[0100] If multiple toner additives are added, the toner additive of the present invention can be selected using methods such as centrifugal separation.

[0101] <Method for measuring the number-average particle size of primary particles in toner additives> The number-average particle size of primary particles of toner additives can be determined by centrifugal sedimentation. Specifically, 0.01 g of dried additive particles were placed in a 25 ml glass vial, and a solution was prepared by adding 0.2 g of 5% Triton solution and 19.8 g of RO water. Next, the probe tip of an ultrasonic disperser was immersed in the above solution, and ultrasonic dispersion was obtained by ultrasonic dispersion at an output of 20 W for 15 minutes. Subsequently, the number-average particle size of primary particles was measured using this dispersion with a CPS Instruments DC24000 centrifugal sedimentation particle size distribution analyzer. The disk rotation speed was set to 18000 rpm, and the true density was set to 1.3 g / cm³. Before measurement, the instrument was calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0102] <Separation of compound A from toner additives> The toner additive is dissolved in toluene and ultrasonically dispersed for 60 minutes, then centrifuged at 3700 rpm for 60 minutes. Leaving the particles settled at the bottom, hexane is transferred to a separate container, fresh hexane is added, ultrasonically dispersed for 30 minutes, and then centrifuged at 3700 rpm for 30 minutes. The hexane is transferred to a separate container, and the remaining particles are dried to obtain the toner additive from which compound A has been removed. Alternatively, compound A can be separated from the hexane transferred to the separate container by vacuum distillation, and the content of compound A in the toner additive can be measured by measuring the mass of the obtained compound A.

[0103] <Method for measuring the melting point of compound A> Measurements are performed using a differential thermal analysis (DSC) analyzer, DSC-7 (manufactured by PerkinElmer). The measurement is carried out in accordance with ASTM D3418-82. 2 to 10 mg of the sample are accurately weighed and placed in an aluminum pan. An empty aluminum pan is used as a reference, and measurements are performed at a heating rate of 10°C / min within the temperature range of 30 to 200°C under normal temperature and humidity conditions. During this heating process, an endothermic peak of the main peak is obtained in the temperature range of 30 to 200°C. The temperature of this endothermic main peak is taken as the melting point of the wax.

[0104] <Method for measuring the surface free energy of compound A> The surface free energy of compound A was measured using the following apparatus, in accordance with the apparatus's operating manual, and using probe liquids (water, diiodomethane, and ethylene glycol) with known surface free energy components, under the following conditions.

[0105] Specifically, a CA-X ROLL contact angle meter manufactured by Kyowa Interface Science Co., Ltd. was used to measure the contact angle θ of each probe liquid on the surface of compound A, and the surface free energy was determined using the Kitazaki-Hata theory equation.

[0106] (i) The detailed measurement conditions for the contact angle θ are as follows: Measurement: Droplet method (circular fitting) Volume: 1 μL Droplet recognition: automatic Image processing: Algorithm - Non-reflection Image Mode: Frame Threshold level: Automatic Furthermore, regarding the contact angle θ, five measurements were taken using each probe liquid, and the average value of these five measurements was used as the contact angle θ for that probe liquid. FAMAS (manufactured by Kyowa Interface Science Co., Ltd.) was used for data analysis.

[0107] <Method for measuring the penetration depth of compound A> Measurements were taken in accordance with JIS K-2235 (1991). Specifically, the sample was heated and melted, placed in a sample container, allowed to cool, and then kept at 25°C in a constant temperature water bath. A specified needle with a total mass of 100g was then inserted vertically into the sample for 5 seconds. The penetration depth of the needle was measured to a depth of 0.1mm and expressed as a dimensionless number obtained by multiplying this value by 10.

[0108] <Method for measuring the BET specific surface area of ​​external additives for toner> The BET specific surface area S can be determined by a low-temperature gas adsorption method using a dynamic constant-pressure method according to the BET method (preferably the BET multi-point method). For example, by using a specific surface area measuring device (product name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation), nitrogen gas is adsorbed onto the sample surface, and the BET specific surface area Y (m²) is measured using the BET multi-point method. 2 It is possible to calculate ( / g).

[0109] Also, the theoretical BET specific surface area X(m 2 The value per g is calculated using the following formula, assuming that the toner additive is a perfect sphere. Theoretical BET specific surface area X = (4 × π × mean circle equivalent diameter A2) / (4 / 3 × π × mean circle equivalent diameter A3 / density) × 1000

[0110] Density required for calculation (cm³) 3 The value of / g) is the true density measured using the dry densimeter Accupic 1330 (manufactured by Shimadzu Corporation).

[0111] <Method for measuring the average pore diameter and pore volume of toner additives> The average pore diameter and total pore volume of the toner additive 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.

[0112] First, approximately 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 average pore diameter 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).

[0113] <Solid 29 Method for measuring the relative abundance of constituent compounds in toner additives 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 toner additives. 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.

[0114] solid 29 The specific measurement conditions for Si-NMR are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DDMAS method 29Si 45° Sample tube: Zirconia 3.2mmφ Sample: Filled in a test tube in powder form. Sample rotation speed: 10kHz Relaxation delay: 180s Scan: 2000

[0115] 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)SiO1 / 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.

[0116] In formulas (S1), (S2), and (S3), Ra, Rb, Rc, Rd, Re, and Rf represent organic groups (e.g., alkyl groups) such as hydrocarbon groups having 1 to 6 carbon atoms, or halogen atoms, bonded to silicon. If further detailed structural analysis is necessary, 29 Along with the Si-NMR measurement results 13 C-NMR and 1 The results of the 1H-NMR measurement may also be used for identification. From the SA, S2, S3, and S4 obtained in this way, S2 / SA, S3 / SA, and S4 / SA are calculated.

[0117] <Method for measuring the degree of compression and cohesiveness of external additives for toners> The degree of compression agglomeration of toner additives is measured using a powder rheometer (FT4, Freeman Technology). First, 10 g of toner additive is weighed into a dedicated cylindrical split container, and the toner additive is compressed at specified pressures (30 kPa, 60 kPa) using a compression test piston attached to the main unit. For the 60 kPa sample, it is left in a dryer set to 100°C for at least one hour immediately before measurement. The compressed additive layer is scraped off at the split portion of the measurement container, removing the upper part of the powder layer. Next, a dedicated needle-shaped jig is attached to the main unit and inserted perpendicularly into the powder layer. The degree of compression agglomeration is obtained by measuring the force of the piercing at this time.

[0118] <Method for measuring the adhesion rate of toner additives to toner particles by water washing method> (Water washing process) A dispersion was prepared by thoroughly mixing a sucrose aqueous solution (made by dissolving 20.7g of sucrose (manufactured by Kishida Chemical Co., Ltd.) in 10.3g of deionized water) and 6mL of Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder) in a 30mL glass vial. For example, a glass vial such as VCV-30 (outer diameter: 35mm, height: 70mm) manufactured by Nichiden Rika Glass Co., Ltd. could be used. 1.0g of toner was added to this dispersion and allowed to stand until the toner naturally settled to prepare the pre-treatment dispersion. This pre-treatment dispersion was shaken for 5 minutes at a shaking speed of 200rpm using a shaker (YS-8D type: manufactured by Yayoi Co., Ltd.) to detach weakly adhering fine particles (external additives for toner) from the surface of the toner particles. Separation of the toner with strongly adhering fine particles remaining from the detached fine particles was performed using a centrifuge. The centrifugal separation process was performed at 3700 rpm for 30 minutes. The toner containing residual fine particles was collected by suction filtration, dried, and washed with water to obtain the toner.

[0119] (Method for measuring the adhesion rate of fine particles) The following is an example of a method for measuring the adhesion rate of fine particles. First, the amount of fine particles contained in the toner particles before water washing is quantified. This is done by measuring the Si element intensity in the toner particles using a wavelength-dispersive X-ray fluorescence analyzer, Axios advanced (PANalytical). Next, the Si element intensity in the toner particles after water washing is measured in the same manner. The adhesion rate (%) is: It can be calculated as (Si element intensity in toner particles after water washing / Si element intensity in toner particles before water washing) × 100.

[0120] [Configurations included in embodiments of the present invention] This embodiment includes the following configuration. (Construction 1) Organosilicon polymer particles having pores, The organosilicon polymer particles contain compound A, which has a melting point of 70°C or higher and 120°C or lower. The surface free energy of compound A is 45 mJ / m 2 An external additive for toner characterized by the following: (Configuration 2) The toner additive according to Configuration 1, wherein compound A is either a hydrocarbon compound or an ester compound. (Configuration 3) An external additive for toner according to Configuration 1 or 2, wherein the penetration of compound A at 25°C is 10 or less. (Configuration 4) An external additive for toner according to any one of Configurations 1 to 3, wherein the content of compound A is 5.0 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of the organosilicon polymer particles. (Configuration 5) The toner additive according to any one of Configurations 1 to 4, wherein the number average particle size of the primary particles of the toner additive is 0.05 μm or more and 0.30 μm or less. (Configuration 6) The BET specific surface area of ​​the toner additive is X (m 2 ( / g), the BET specific surface area of ​​the toner additive obtained by washing the toner additive with hexane is Y(m²). 2 ( / g), the theoretical BET specific surface area calculated from the particle size of the toner additive after washing is Z(m 2 When we set it to / g, An external toner additive described in any of configurations 1 to 5 that satisfies the following formulas (i) and (ii). (i) 2.0 ≤ Y / X (ii) 3.0 ≤ Y / Z ≤ 9.0 (Configuration 7) The total pore volume of the external additive for toner after washing is 0.30 cm³ 3 / g or more 1.00cm 3 Toner additives described in composition 6 that are less than or equal to / g. (Configuration 8) The toner additive according to Configuration 6, wherein the volume average diameter of the pores of the toner additive after cleaning is 5 nm or more and 20 nm or less. (Configuration 9) The external additive for toner 29 In a chart obtained by Si-NMR measurement, when the total peak area attributed to the silicon polymer is denoted as SA and the peak area attributed to the D unit structure is denoted as S2, the toner additive according to any of configurations 1 to 8 satisfies the following formula for SA and S2. 0.20 ≤ S² / SA ≤ 0.70 (Configuration 10) The toner external additive 29In the chart obtained by Si-NMR measurement, when the peak area attributed to the Q unit structure is denoted as S4 and the peak area attributed to the T unit structure is denoted as S3, then SA, S3 and S4 are 0.20 ≤ S4 / SA ≤ 0.60 0.00 ≤ S3 / SA ≤ 0.50 An external additive for toner described in configuration 9 that satisfies the requirements. (Configuration 11) The toner additive is (i) The degree of compression cohesiveness at 25℃ and 30kPa is 20mJ or more and 70mJ or less, (ii) The degree of compression cohesiveness at 100°C and 60kPa is between 120mJ and 180mJ. An external additive for toner described in any of components 1 to 10. (Configuration 12) A toner having toner particles and an external additive for toner, A toner characterized in that the toner additive is the toner additive described in any of the components 1 to 11. (Configuration 13) The toner according to Configuration 12, wherein the toner additive is contained in an amount of 0.1 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of the toner particles. (Configuration 14) The toner according to Configuration 12 or 13, wherein the adhesion rate of the toner additive to the toner particles is 50% or more, based on the mass of the toner. [Examples]

[0121] 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.

[0122] <Manufacturing example of toner additive 1> 1. Hydrolysis process 43.2 g of RO water and 0.008 g of acetic acid as a catalyst were charged into a 200 ml beaker and stirred at 45°C. 27.2 g of tetraethoxysilane and 27.2 g of dimethyldimethoxysilane were added and stirred for 1.5 hours to obtain the raw material solution.

[0123] 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 the above hydrolysis step was added dropwise over 1 minute. The mixture after the addition of the raw material solution was stirred at 30°C for 1.0 hour to allow the polycondensation reaction to proceed and obtain a polycondensation reaction solution.

[0124] 3.Particleization process 1000g of RO water was placed in a 2000ml beaker, and the polycondensation reaction solution obtained in the above condensation polymerization step 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.

[0125] 4. Filtration process A dispersion containing silicon polymer particles having siloxane bonds, obtained in the above particle formation process, 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.

[0126] 5. Post-processing steps 10 g of the fine particles obtained in the above filtration step and 100 g of toluene were added to a 100 ml beaker and dispersed. Then, 1 g of paraffin wax HNP-10 (manufactured by Nippon Seiro Co., Ltd.) was added and the mixture was stirred at 60°C for 2 hours. The dispersion was removed by vacuum distillation to remove the solvent, and dried at 50°C for 24 hours to obtain toner additive 1. The number-average primary particle size of toner additive 1 was 0.12 μm. The physical properties of toner additive 1 are shown in Table 1. In Table 1, "Compound A content (parts by mass)" indicates the amount of compound A per 100 parts by mass of fine particles (organosilicon polymer particles).

[0127] <Manufacturing example of toner additive 2> Except for changing the stirring temperature of the mixture after the raw material solution was added dropwise in the condensation polymerization process to 25°C and changing the amount of paraffin wax used in the post-treatment process to 0.6 g, toner additive 2 was obtained in the same manner as the production example of toner additive 1. The physical properties of the obtained toner additive 2 are shown in Table 1.

[0128] <Manufacturing example of toner additive 3> Except for changing the stirring time to 0.5 hours in the condensation polymerization process, toner additive 3 was obtained in the same manner as in the production example of toner additive 2. The physical properties of the obtained toner additive 3 are shown in Table 1.

[0129] <Manufacturing example of toner additive 4> Except for changing the amount of tetraethoxysilane to 22.3 g, trimethoxymethylsilane to 9.7 g, and dimethyldimethoxysilane to 21.5 g in the hydrolysis step, and changing the amount of paraffin wax used in the post-treatment step to 1.5 g, toner additive 4 was obtained in the same manner as the production example of toner additive 1. The physical properties of the obtained toner additive 4 are shown in Table 1.

[0130] <Manufacturing example of toner additive 5> Except for changing the amount of silicone oil used in the oil treatment process to 1.8 g, toner additive 5 was obtained in the same manner as the manufacturing example of toner additive 4. The physical properties of the obtained toner additive 5 are shown in Table 1.

[0131] <Manufacturing example of toner additive 6> Except for changing the amount of tetraethoxysilane to 22.3 g, trimethoxymethylsilane to 24.3 g, and dimethyldimethoxysilane to 8.6 g in the hydrolysis step, toner additive 6 was obtained in the same manner as in the production example of toner additive 1. The physical properties of the obtained toner additive 6 are shown in Table 1.

[0132] <Manufacturing example of toner additive 7> Except for changing the amount of tetraethoxysilane to 44.6 g and the amount of dimethyldimethoxysilane to 17.2 g in the hydrolysis step, toner additive 7 was obtained in the same manner as in the production example of toner additive 1. The physical properties of the obtained toner additive 7 are shown in Table 1.

[0133] <Manufacturing example of toner additive 8> Except for changing the amount of tetraethoxysilane to 63.2 g and dimethyldimethoxysilane to 6.4 g in the hydrolysis step, toner additive 8 was obtained in the same manner as in the production example of toner additive 1. The physical properties of the obtained toner additive 8 are shown in Table 1.

[0134] <Manufacturing example of toner additive 9> Except for changing the amount of tetraethoxysilane to 22.3 g and dimethyldimethoxysilane to 30.0 g in the hydrolysis step, and changing the amount of 28% aqueous ammonia in the condensation polymerization step to 1.5 g, toner additive 9 was obtained in the same manner as in the production example of toner additive 1. The physical properties of the obtained toner additive 9 are shown in Table 1.

[0135] <Manufacturing example of toner additive 10> Except for changing the amount of tetraethoxysilane to 68.4 g and dimethyldimethoxysilane to 3.4 g in the hydrolysis step, toner additive 10 was obtained in the same manner as in the production example of toner additive 1. The physical properties of the obtained toner additive 10 are shown in Table 1.

[0136] <Manufacturing example of toner additive 11> Except for changing the amount of tetraethoxysilane to 14.9 g and the amount of dimethyldimethoxysilane to 34.3 g in the hydrolysis step, toner additive 11 was obtained in the same manner as in the production example of toner additive 1. The physical properties of the obtained toner additive 11 are shown in Table 1.

[0137] <Manufacturing example of toner additive 12> Except for changing the amount of 28% aqueous ammonia in the condensation polymerization step to 2.5 g, toner additive 12 was obtained in the same manner as the manufacturing example of toner additive 10. The physical properties of the obtained toner additive 12 are shown in Table 1.

[0138] <Manufacturing example of toner additive 13> Except for changing the stirring temperature to 25°C during the condensation polymerization process, the toner additive 13 was obtained in the same manner as the production example of toner additive 9. The physical properties of the obtained toner additive 13 are shown in Table 1.

[0139] <Manufacturing example of toner additive 14> Except for the addition of 48.6 g of trimethoxymethylsilane instead of tetraethoxysilane and dimethyldimethoxysilane in the hydrolysis step, and the change in stirring temperature to 30°C and stirring time to 0.5 hours, toner additive 14 was obtained in the same manner as the production example of toner additive 1. The physical properties of the obtained toner additive 14 are shown in Table 1.

[0140] <Manufacturing example of toner additive 15> Except for changing the stirring time to 2 hours in the hydrolysis process, the toner additive 15 was obtained in the same manner as the manufacturing example of the toner additive 12. The physical properties of the obtained toner additive 15 are shown in Table 1.

[0141] <Manufacturing example of toner additive 16> Except for changing the stirring time to 2.5 hours in the hydrolysis process, toner additive 16 was obtained in the same manner as the manufacturing example of toner additive 15. The physical properties of the obtained toner additive 16 are shown in Table 1.

[0142] <Manufacturing example of toner additive 17> Toner additive 17 was obtained in the same manner as in the manufacturing example of toner additive 1, except that the stirring time in the hydrolysis process was changed to 1 hour. The physical properties of the obtained toner additive 17 are shown in Table 1.

[0143] <Manufacturing example of toner additive 18> Except for changing the stirring time to 45 minutes in the hydrolysis process, the toner additive 18 was obtained in the same manner as the manufacturing example of toner additive 17. The physical properties of the obtained toner additive 18 are shown in Table 1.

[0144] <Manufacturing example of toner additive 19> Except for changing the amount of paraffin wax used in the post-processing step to 0.5 g, toner additive 19 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 19 are shown in Table 1.

[0145] <Manufacturing example of toner additive 20> Except for changing the amount of paraffin wax used in the post-processing step to 0.3 g, toner additive 20 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 20 are shown in Table 1.

[0146] <Manufacturing example of toner additive 21> Except for changing the amount of paraffin wax used in the post-processing step to 2.0 g, toner additive 21 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 21 are shown in Table 1.

[0147] <Manufacturing example of toner additive 22> Except for changing the amount of paraffin wax used in the post-processing step to 2.5 g, toner additive 22 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 22 are shown in Table 1.

[0148] <Manufacturing example of toner additive 23> Except for using rice wax A-1 (manufactured by Cerarica NODA Co., Ltd.) instead of paraffin wax in the post-processing step, toner additive 23 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 23 are shown in Table 1.

[0149] <Manufacturing example of toner additive 24> Except for changing the paraffin wax used in the post-processing step to SP-0160 (manufactured by Nippon Seiro Co., Ltd.), toner additive 24 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 24 are shown in Table 1.

[0150] <Manufacturing example of toner additive 25> Except for using microcrystalline wax Hi-Mic-1070 (manufactured by Nippon Seiro Co., Ltd.) instead of paraffin wax in the post-processing step, toner additive 25 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 25 are shown in Table 1.

[0151] <Manufacturing example of toner additive 26> Except for using carnauba wax EMUSTAR-0413 (manufactured by Nippon Seiro Co., Ltd.) instead of paraffin wax in the post-processing step, toner additive 26 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 26 are shown in Table 1.

[0152] <Manufacturing example of toner additive 27> 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 this 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.

[0153] To the dispersion of silicon polymer particles having siloxane bonds obtained in the above process, 150.0 g of hexamethyldisilazane was added at room temperature. Then, the dispersion was 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 (silica particles).

[0154] The obtained fine particles were post-treated with paraffin wax HNP-10 in the same manner as toner additive 1 to obtain toner additive 27. The physical properties of the obtained toner additive 27 are shown in Table 1.

[0155] <Manufacturing example of toner additive 28> Except for the absence of a post-processing step, the toner additive 28 was obtained in the same manner as the manufacturing example of the toner additive 27. The physical properties of the obtained toner additive 28 are shown in Table 1.

[0156] <Manufacturing example of toner additive 29> Except for the absence of a post-processing step, toner additive 29 was obtained in the same manner as the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 29 are shown in Table 1.

[0157] <Manufacturing example of toner additive 30> Except for changing the paraffin wax used in the post-processing step to ParaffinWax-135 (manufactured by Nippon Seiro Co., Ltd.), toner additive 30 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 30 are shown in Table 1.

[0158] <Manufacturing example of toner additive 31> Except for using a resin-based wax, POLYCOAT-3155 (manufactured by Nippon Seiro Co., Ltd.), instead of paraffin wax in the post-processing step, toner additive 31 was obtained in the same manner as in the manufacturing example of toner additive 1. The physical properties of the obtained toner additive 31 are shown in Table 1.

[0159] [Table 1]

[0160] <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) • 8.0 parts (0.054 moles) of adipic acid • Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter four-necked glass flask, and a thermometer, stirring rod, condenser, and nitrogen inlet tube were attached and placed 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, which is the binder resin component. The acid value of this polyester resin A1 was 5 mg KOH / g.

[0161] <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.

[0162] <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, the mixture was kneaded in a twin-shaft kneader (PCM-30 model, manufactured by Ikegai Co., Ltd.) set to a temperature of 125°C and a rotation speed of 300 rpm. The resulting mixture was cooled and coarsely ground to a diameter of 1 mm or less using a hammer mill to obtain coarse material. The obtained coarse material was finely ground using a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.). Further classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions for the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were a classification rotor rotation speed of 50.0 s. -1 Classification was performed. The resulting toner particles 1 had a weight-average particle size (D4) of 5.9 μm.

[0163] <Example of Toner 1 manufacturing> • Toner particles 1 100 copies • Toner additive particles 1 6.0 parts The above ingredients were mixed in a Henschel FM-10C mixer (manufactured by Mitsui Miike Chemical Machinery) at a rotation speed of 30 seconds. -1 The mixture was then mixed for a rotation time of 10 minutes to obtain toner particle mixture 1.

[0164] (Heat treatment process) The obtained toner particle mixture 1 was subjected to heat treatment using the surface treatment apparatus shown in Figure 1 to obtain toner 1. The physical properties of toner 1 are shown in Table 2. The operating conditions for the heat treatment were a feed rate of 2 kg / hr, a hot air temperature of 150°C, and a hot air flow rate of 6 m³. 3 / min., cold air temperature = -5℃, cold air flow rate = 2.5m 3 / min., blower airflow = 11m 3 / min., injection air flow rate = 1m 3 I set it to / min.

[0165] <Manufacturing examples for toners 2-37> In the manufacturing example of Toner 1, the toner particles, external additives for toner, and the presence or absence of a hot air treatment process, as well as the hot air temperature in the heat treatment process, were changed to those listed in Table 2, and Toners 2 to 37 were obtained in the same manner. The physical properties of Toners 2 to 37 are shown in Table 2.

[0166] [Table 2]

[0167] <Example of manufacturing for Carrier 1> • Number-average particle size 0.30 μm, magnetization strength 65 Am under a magnetic field of (1000 / 4π (kA / m)) 2 Magnetite ( / kg) • Number-average particle size 0.50 μm, magnetization strength 65 Am under a magnetic field of (1000 / 4π (kA / m)) 2 Magnetite ( / kg) Each of the above materials was treated by adding 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) to the mixture and stirring at high speed in a container at over 100°C to process the respective fine particles.

[0168] • 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: 58% by mass • Magnetite treated with the above silane compound: 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 maintained therefor. 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 the mixture was air-dried. This was then dried under reduced pressure (5 mmHg or less) at a temperature of 60°C to obtain spherical carrier 1 with magnetic dispersion. The volume-based 50% particle size (D50) was 34.2 μm.

[0169] <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.

[0170] <Manufacturing examples of two-component developers 2-37> 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 37 were obtained.

[0171] [Table 3]

[0172] [Example 1] <Toner Evaluation Method> As the image forming apparatus, a modified Canon imagePRESS C810 digital commercial printer was used, and a two-component developer 1 was placed in the cyan developer unit. The modifications to the apparatus included allowing free setting of the fixing temperature, process speed, DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power. For image output evaluation, a solid fill image (FFh image) with the desired image ratio was output, and VDC, VD, and laser power were adjusted so that the amount of toner on the FFh image on the paper was as desired, and the evaluation described below was performed.

[0173] FFh is a hexadecimal value representing 256 gradations, where 00h is the first gradation (white area) of the 256 gradations, and FFh is the 256th gradation (solid area).

[0174] The evaluation was conducted based on the following evaluation method, and the results are shown in Table 4.

[0175] [Abrasion resistance] • Paper: Image Coat Gloss 158 (158.0g / m²) 2 ) (Sold by Canon Marketing Japan Inc.) • Amount of toner on paper: 0.05 mg / cm² 2 (Image 2Fh) (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) • Evaluation image: Place a 3cm x 15cm image in the center of the A4 paper shown above. • Fixation test environment: Normal temperature and humidity environment (temperature 23°C / humidity 50%RH (hereinafter N / N)) Fixing temperature: 180℃ • Process speed: 377 mm / sec The above evaluation images were output, and the abrasion resistance was assessed. The difference in reflectance was used as the evaluation index for abrasion resistance.

[0176] First, a JSPS-type friction fastness tester (AB-301: manufactured by Tester Sangyo Co., Ltd.) is used to apply a load of 0.5 kgf to the image portion of the evaluation image, and a new evaluation paper is rubbed against it (10 back-and-forth strokes). Then, a reflectometer (REFLECTOMETER MODEL TC-6DS: manufactured by Tokyo Denshoku Co., Ltd.) is used to measure the reflectance of the rubbed portion of the new evaluation paper and the reflectance of the unrubbed portion.

[0177] Then, the difference in reflectance before and after friction was calculated using the following formula. The obtained difference in reflectance was evaluated according to the following evaluation criteria. A rank of F or higher indicates that the effects of the present invention have been achieved. Difference in reflectance = Reflectance before friction - Reflectance after friction (Evaluation Criteria) 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 and less than 3.0% F: 3.0% or more and less than 4.0% G:4.0% or more

[0178] [Heat resistance and pressure resistance] ·Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Toner amount on paper: 0.80 mg / cm² 2 (FFh image) • Evaluation image: Place a 6.0cm x 5.0cm image in the center of the A4 paper shown above. Fixing temperature: 180℃ The above evaluation image was printed, and its heat resistance and pressure resistance were evaluated. The image portion of the fixing image paper was placed face down, and an unused sheet of paper (GFC-081 (81.0 g / m²) was used. 2 )) 100 sheets were placed on top of the fixing image paper, and then 2500 sheets of the same type of unused paper were placed on top of the fixing image paper, sandwiching the fixing image paper. This was left to stand in a constant temperature bath heated to 55°C for 24 hours, and then removed from the constant temperature bath. The reflectance of the unused paper that had been in contact with the fixing image paper was measured in the portion that was in contact with the image area. The color transfer of the image was measured by subtracting the reflectance of the portion of the unused paper that was not in contact with the image area from the obtained reflectance. The heat resistance of the image was evaluated from the reflectance after the subtraction according to the following criteria. The reflectance was measured using TC-6DS (manufactured by Tokyo Denshoku). A rank of F or higher indicates that the effects of the present invention have been achieved.

[0179] (Evaluation Criteria) A: The reflectance after subtraction is less than 2.0% B: The reflectance after subtraction is 2.0% or more and less than 3.0%. C: The reflectance after subtraction is 3.0% or more and less than 5.0%. D: The reflectance after subtraction is 5.0% or more and less than 7.0%. E: Net reflectance is 7.0% or more and less than 9.0% F: Net reflectance is 9.0% or more and less than 11.0% G: The reflectance after subtraction is 11.0% or higher.

[0180] [Durability] ·Paper: CS-680 (68.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Amount of toner on paper: 0.35 mg / cm² 2 (FFh image) • Evaluation image: Chart with 100% aspect ratio of the above A4 paper image. • Fixation test environment: High temperature and high humidity environment: Temperature 30°C / Humidity 85%RH (hereinafter referred to as "H / H") As a durability image output test, 10,000 copies of a band chart with FFh output and an image ratio of 0.1% were printed on A4 paper. Afterward, the evaluation images were printed, and the number of white spots in the images was visually checked. A rank of F or higher indicates that the effects of the present invention have been achieved.

[0181] (Evaluation Criteria) A: Fewer than 5 white spots B: 5 to 10 white spots C: 10 to less than 15 white spots D: 15 to less than 20 white spots E: 20 to less than 25 white spots F: 25 to less than 30 white spots G: More than 30 white spots

[0182] [Examples 2-32] Two-component developers 2 to 32 were evaluated in the same manner as in Example 1. The evaluation results for Examples 2 to 32 are shown in Table 4.

[0183] [Comparative Examples 1-5] Two-component developers 33-37 were evaluated in the same manner as in Example 1. The evaluation results for Comparative Examples 1-5 are shown in Table 4.

[0184] [Table 4] [Explanation of symbols]

[0185] 1. Raw material quantitative supply means, 2. Compressed gas flow rate adjustment means, 3. Inlet pipe, 4. Protruding member, 5. Supply pipe, 6. Processing chamber, 7. Hot air supply means, 8. Cold air supply means, 9. Regulating means, 10. Recovery means, 11. Hot air supply means outlet, 12. Distribution member, 13. Swirling member, 14. Powder particle supply port

Claims

1. Organosilicon polymer particles having pores, The organosilicon polymer particles contain compound A, which has a melting point of 70°C or higher and 120°C or lower. The surface free energy of compound A is 45 mJ / m 2 An external additive for toner characterized by the following:

2. The toner additive according to claim 1, wherein compound A is either a hydrocarbon compound or an ester compound.

3. The toner additive according to claim 1 or 2, wherein the penetration of compound A at 25°C is 10 or less.

4. The toner additive according to claim 1 or 2, wherein the content of compound A is 5.0 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of the organosilicon polymer particles.

5. The toner additive according to claim 1 or 2, wherein the number-average particle size of the primary particles of the toner additive is 0.05 μm or more and 0.30 μm or less.

6. The BET specific surface area of ​​the toner additive is X (m²). 2 ( / g), the BET specific surface area of ​​the toner additive after washing with hexane is Y (m²) 2 ( / g), the theoretical BET specific surface area calculated from the particle size of the toner additive after washing is Z (m 2 When / g) An external additive for toner according to claim 1 or 2, satisfying the following formulas (i) and (ii). (i) 2.0≦Y / X (ii) 3.0≦Y / Z≦9.0

7. The total pore volume of the toner additive after washing is 0.30 cm³. 3 / g or more 1.00cm 3 The toner additive according to claim 6, wherein the amount is less than or equal to / g.

8. The toner additive according to claim 6, wherein the volume average diameter of the pores of the toner additive after washing is 5 nm or more and 20 nm or less.

9. The above-mentioned external additive for toner 29 In a chart obtained by Si-NMR measurement, when the total peak area attributed to silicon polymers is denoted as SA and the peak area attributed to D unit structures is denoted as S2, the toner additive according to claim 1 or 2 satisfies the following formula for SA and S2. 0.20 ≤ S² / SA ≤ 0.70

10. The above-mentioned external additive for toner 29 In a chart obtained by Si-NMR measurement, when the peak area attributed to the Q unit structure is denoted as S4 and the peak area attributed to the T unit structure is denoted as S3, then SA, S3, and S4 are 0.20 ≤ S4 / SA ≤ 0.60 0.00 ≤ S3 / SA ≤ 0.50 An external additive for toner according to claim 9, which satisfies the requirements.

11. The aforementioned toner additive is (i) The degree of compression cohesiveness at 25°C and 30 kPa is 20 mJ or more and 70 mJ or less, (ii) The degree of compression cohesiveness at 100°C and 60 kPa is 120 mJ or more and 180 mJ or less. An external additive for toner according to claim 1 or 2.

12. A toner having toner particles and an external additive for toner, A toner characterized in that the toner additive is the toner additive described in claim 1 or 2.

13. The toner according to claim 12, wherein the toner additive is contained in an amount of 0.1 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of the toner particles.

14. The toner according to claim 12, wherein the adhesion rate of the toner additive to the toner particles is 50% or more, based on the mass of the toner.

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