Core-shell type particle and tower

Abstract

To provide core-shell type particles that are highly effective as a mold release agent because the mold release agent can ooze out even with lighter pressure during fixing.SOLUTION: Core-shell type particles have a core and a shell on the surface of the core. The core contains a crystalline mold release agent. A sum of the number average value and standard deviation of a Feret diameter of the particles is 20 to 500 nm. The shell comprises an organosilicon polymer. In differential scanning calorimetry of the particles, a maximum endothermic peak exists when a temperature is raised from 30°C to 120°C at a rate of 10.0°C / min, a maximum exothermic peak exists when the temperature is lowered from 120°C to 30°C at a rate of 10.0°C / min, and when a peak temperature of the maximum endothermic peak is Tm (°C) and a peak temperature of the maximum exothermic peak is Tc (°C), the Tc is lower than the Tm by 5°C or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to core-shell type particles and toner used in recording methods such as electrophotography, which use these particles as an external additive. [Background technology]

[0002] In recent years, image forming equipment such as photocopiers and printers have seen increasing diversification in their intended use and operating environments, and there is a growing demand for even higher speeds and longer lifespans. Numerous methods are known for image formation, but electrophotography is one of the major techniques. The electrophotographic process is as follows: First, an electrostatic latent image is formed on an electrostatic image carrier (hereinafter also called a "photoreceptor") by various means. Next, the latent image is developed with a developer (hereinafter also called a "toner") to become a visible image, and if necessary, the toner image is transferred to a recording medium such as paper. Finally, the toner image is fixed onto the recording medium by heat or pressure to obtain a copy. In particular, when fixing a toner image onto a recording medium, if a method is used in which the toner image is fused to the recording medium with a heated roller, a method is known in which a release agent is embedded in the toner particles to prevent the toner from fusing to the roller.

[0003] However, when a release agent is encapsulated within toner particles, only a portion of the total release agent can seep to the toner surface during fixing and contribute to release; the rest remains inside the toner particles without contributing to release. In particular, as the fixing process becomes faster, the proportion of release agent that can seep to the toner surface and contribute to release during fixing becomes even smaller. Therefore, toner particles need to contain more release agent to achieve both high speed and sufficient release properties. On the other hand, when the content of the release agent increases, member contamination caused by the release agent occurs during long-term use, and image quality degradation is likely to occur. That is, due to the stress associated with the rubbing of the toner and the member, some of the toner cracks, and the contained release agent is exposed and adheres to the member, resulting in image quality degradation such as image streaks. Furthermore, since the stress on the toner increases with the increase in speed, it has been difficult to achieve both high speed and long life. Therefore, a technique has been proposed to increase the proportion of the release agent that can penetrate the toner surface during fixing.

[0004] In Patent Document 1, a technique is disclosed in which a release agent is disposed near the toner surface to facilitate the release agent from bleeding out to the toner surface. In Patent Document 2, a technique is disclosed in which a release agent is embedded in the toner surface and a film of a silane coupling agent is formed on the toner surface. In Patent Document 3, a toner having a core-shell type external additive, that is, an external additive in which a release agent is used as a core and the surface layer is coated with a shell of an organosilicon polymer, is disclosed. An organosilicon compound having a methacryloyl group is used for the organosilicon polymer.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] According to the invention of Patent Document 1, the total content of the release agent can be reduced. However, the release agent Placing the release agent on the toner surface increases the likelihood of material contamination, thus failing to fully achieve both high speed and long lifespan. In the invention described in Patent Document 2, for the release agent embedded on the toner surface to penetrate the silane coupling agent film and seep out, volume compression due to deformation of the toner particles is necessary. Therefore, the release agent is less likely to seep out in the temperature range where the deformation of toner particles is small, which is the initial temperature range at which the toner particles can be fixed. In other words, even though the release agent is placed close to the toner surface, a large amount of release agent is required to obtain sufficient release properties from the initial temperature range at which the toner can be fixed. The invention described in Patent Document 3 allows the release agent to be placed on the toner surface, and the organosilicon polymer shell suppresses contamination of the material due to the exposure of the release agent. Furthermore, when the core release agent melts, the organosilicon polymer shell is subjected to pressure that causes it to quickly seep out as the core deforms, so the release agent can be released regardless of the core's fixing temperature. However, a certain level of pressure is required for the release agent inside the external additive to seep out during fixing, meaning that only external additives that are subjected to sufficient pressure can contribute to release. Furthermore, to improve durability, the organosilicon polymer shell needs to be strengthened, which further reduces the proportion of external additive that can contribute to release. For these reasons, there is room for improvement in its effectiveness as a release agent. This disclosure provides core-shell type particles that allow the release agent to seep out even under lighter pressure and have high effectiveness as a release agent. This disclosure also provides a toner using these core-shell type particles as an external additive. [Means for solving the problem]

[0007] This disclosure relates to a core-shell type particle having a core and a shell on the surface of the core, The core contains a crystalline release agent, The sum of the number mean and standard deviation of the Ferret diameter of the particles is between 20 and 500 nm. The shell contains an organosilicon polymer, In differential scanning calorimetry of the particles, When the temperature is increased from 30°C to 120°C at a rate of 10.0°C / min, a maximum endothermic peak is observed. The maximum heat generation peak occurred when the temperature was reduced from 120°C to 30°C at a rate of 10.0°C / min. When the peak temperature of the maximum endothermic peak is denoted as Tm (°C) and the peak temperature of the maximum exothermic peak is denoted as Tc (°C), if Tc is 5°C or more lower than Tm, Regarding core-shell type particles.

[0008] Furthermore, another aspect of the present disclosure is a core-shell type particle having a core and a shell on the surface of the core, The core contains hydrocarbon wax, The sum of the number mean and standard deviation of the Ferret diameter of the particles is between 20 and 500 nm. The shell contains an organosilicon polymer, In differential scanning calorimetry of the particles, When the temperature is increased from 30°C to 120°C at a rate of 10.0°C / min, a maximum endothermic peak is observed. The maximum heat generation peak occurred when the temperature was reduced from 120°C to 30°C at a rate of 10.0°C / min. When the peak temperature of the maximum endothermic peak is denoted as Tm (°C) and the peak temperature of the maximum exothermic peak is denoted as Tc (°C), if Tc is 5°C or more lower than Tm, Regarding core-shell type particles.

[0009] Furthermore, yet another aspect of this disclosure is a core-shell type particle having a core and a shell on the surface of the core, The core contains hydrocarbon wax, The sum of the number mean and standard deviation of the Ferret diameter of the particles is between 20 and 500 nm. The shell contains an organosilicon polymer, The organosilicon polymer contains a structure represented by the following formula (RT3): Core-shell type particles. R-SiO 3 / 2 ...(RT3) [In formula (RT3), R represents an alkyl group having 1 to 6 carbon atoms.] [Effects of the Invention]

[0010] This disclosure makes it possible to provide core-shell type particles that allow the release agent to seep out even under lighter pressure and have high effectiveness as a release agent. [Brief explanation of the drawing]

[0011] [Figure 1] Schematic diagram of a device for measuring triboelectric charge. [Modes for carrying out the invention]

[0012] In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be combined in any way.

[0013] This disclosure relates to a core-shell type particle having a core and a shell on the surface of the core, The core contains a crystalline release agent, The sum of the number mean and standard deviation of the Ferret diameter of the particles is between 20 and 500 nm. The shell contains an organosilicon polymer, In differential scanning calorimetry of the particles, When the temperature is increased from 30°C to 120°C at a rate of 10.0°C / min, a maximum endothermic peak is observed. The maximum heat generation peak occurred when the temperature was reduced from 120°C to 30°C at a rate of 10.0°C / min. When the peak temperature of the maximum endothermic peak is denoted as Tm (°C) and the peak temperature of the maximum exothermic peak is denoted as Tc (°C), if Tc is 5°C or more lower than Tm, Regarding core-shell type particles.

[0014] The inventors have found that by using the above-described configuration, the release agent can seep out even under light pressure, such as during fixing, and that it is possible to provide core-shell type particles with high effectiveness as a release agent. The reason for this is hypothesized as follows. In differential scanning calorimetry (DSC measurement) using the above-described core-shell type particles as a sample, the endothermic peak during heating indicates the melting of the crystalline release agent contained in the core. Subsequently, the exothermic peak during cooling indicates the solidification of the melted release agent. For the same substance, melting and solidification occur at the same temperature, and in actual measurements, due to the time lag in the signal response of the DSC measuring instrument, the melting temperature is observed to be higher and the solidification temperature to be observed to be lower.

[0015] When DSC measurements are performed under conditions where the heating and cooling rates are 10°C / min, the solidification temperature is observed to be 2-3°C lower than the melting temperature. If the solidification temperature is 5°C or more lower than the melting temperature, it is thought that the crystalline release agent became compatible with the organosilicon polymer shell when it melted, causing a freezing point depression. For example, when exposed to high temperatures such as during fixing, the crystalline release agent and the organosilicon polymer shell become compatible, causing the shell to soften and the particles to become more easily deformed, while the melted release agent can easily seep out from the parts where compatibility has progressed. Here, the release agent is defined as having a kinematic viscosity of 100 mm at 110°C. 2 This refers to substances with a kinematic viscosity of less than / second. Release agents with such kinematic viscosity are likely to flow out from the part that is compatible with the organosilicon polymer shell during fixing, and it is thought that the release agent can seep out even under light pressure.

[0016] Furthermore, the sum of the number mean and standard deviation of the Ferret diameter of core-shell type particles (hereinafter also referred to as "maximum Ferret diameter") is between 20 and 500 nm. When the maximum Ferret diameter is 20 nm or more, it is possible to encapsulate the amount of release agent necessary for compatibility, and when the maximum Ferret diameter is 500 nm or less, it is possible to form a strong organosilicon polymer shell necessary to improve durability.

[0017] Furthermore, another aspect of the present disclosure is a core-shell type particle having a core and a shell on the surface of the core, The core contains hydrocarbon wax, The sum of the number mean and standard deviation of the Ferret diameter of the particles is between 20 and 500 nm. The shell contains an organosilicon polymer, In differential scanning calorimetry of the particles, When the temperature is increased from 30°C to 120°C at a rate of 10.0°C / min, a maximum endothermic peak is observed. The maximum heat generation peak occurred when the temperature was reduced from 120°C to 30°C at a rate of 10.0°C / min. When the peak temperature of the maximum endothermic peak is denoted as Tm (°C) and the peak temperature of the maximum exothermic peak is denoted as Tc (°C), if Tc is 5°C or more lower than Tm, Regarding core-shell type particles.

[0018] The inventors have found that by using the above-described configuration, hydrocarbon wax can seep out even under light pressure, such as during fixing, and that core-shell type particles with high effectiveness as a mold release agent can be provided. The reason for this is hypothesized as follows.

[0019] In DSC measurements using the above-described core-shell type particles as a sample, the endothermic peak during heating indicates the melting of the hydrocarbon wax contained in the core. Next, the exothermic peak during cooling indicates the solidification of the melted hydrocarbon wax. If the solidification temperature is 5°C or more lower than the melting temperature, it is considered that the hydrocarbon wax became miscible with the organosilicon polymer shell when it melted, resulting in a freezing point depression. When exposed to high temperatures, such as during fixing, the hydrocarbon wax and the organosilicon polymer shell become compatible, causing the shell to soften and the particles to deform more easily. At the same time, the molten hydrocarbon wax can easily seep out from the areas where compatibility has progressed. Since the molten hydrocarbon wax has good wettability with the organosilicon polymer shell, it is thought that it can easily wet and spread outwards from the compatible areas with the organosilicon polymer shell, allowing the hydrocarbon wax to seep out even under light pressure.

[0020] Furthermore, the maximum ferret diameter of core-shell type particles is 20 to 500 nm. When the maximum ferret diameter is 20 nm or more, it is possible to encapsulate the amount of hydrocarbon wax necessary for compatibility, and when the maximum ferret diameter is 500 nm or less, it is possible to form a strong organosilicon polymer shell necessary to improve durability.

[0021] Furthermore, yet another aspect of this disclosure is a core-shell type particle having a core and a shell on the surface of the core, The core contains hydrocarbon wax, The sum of the number mean and standard deviation of the Ferret diameter of the particles is between 20 and 500 nm. The shell contains an organosilicon polymer, The organosilicon polymer contains a structure represented by the following formula (RT3): Core-shell type particles. R-SiO 3 / 2 ...(RT3) [In formula (RT3), R represents an alkyl group having 1 to 6 carbon atoms.]

[0022] The inventors have found that by using the above configuration, carbonization can be achieved even with light pressure, such as during fixing. We discovered that hydrogen wax can leach out, providing core-shell type particles with high efficacy as hydrocarbon wax. We hypothesize the following reason for this:

[0023] The hydrocarbon wax and the organosilicon polymer having the structure represented by (RT3) exhibit mutual compatibility due to the structural similarity between the R alkyl group and the hydrocarbon wax. When exposed to high temperatures, such as during fixing, the hydrocarbon wax and the organosilicon polymer shell having the structure represented by (RT3) become compatible, causing the shell to soften and the particles to become more deformable. At the same time, the molten hydrocarbon wax can easily seep out from the areas where compatibility has progressed. Because the molten hydrocarbon wax has good wettability with the shell of the organosilicon polymer, it is thought that it can easily wet and spread to the outside from the miscible portion with the organosilicon polymer having the structure represented by (RT3), and that the hydrocarbon wax can seep out even under light pressure.

[0024] Furthermore, the maximum ferret diameter of core-shell type particles is 20 to 500 nm. When the maximum ferret diameter is 20 nm or more, it is possible to encapsulate the amount of hydrocarbon wax necessary for compatibility, and when the maximum ferret diameter is 500 nm or less, the required durability can be ensured by forming an organosilicon polymer shell with a structure represented by (RT3).

[0025] The embodiments of the present disclosure described above will be explained below. As stated above, core-shell type particles have high effectiveness as release agents and also possess durability. For this reason, they are suitable for use as external additives for toners, for example, by adding them to toner particles. Below, external additives for toners will be used as an example of core-shell type particles.

[0026] The sum of the number mean and standard deviation of the Ferret diameter of core-shell type particles (maximum Ferret diameter) is 20 to 500 nm. This maximum Ferret diameter is preferably 50 to 400 nm, more preferably 80 to 300 nm, even more preferably 100 to 200 nm, and even more preferably 120 to 180 nm. The maximum Ferret diameter can be controlled by the size of the particles used in the core and the thickness of the shell formed.

[0027] In DSC measurements of core-shell type particles, a maximum endothermic peak is observed when the temperature is increased from 30°C to 120°C at a rate of 10.0°C / min, and a maximum exothermic peak is observed when the temperature is decreased from 120°C to 30°C at a rate of 10.0°C / min. Furthermore, when the peak temperature of the maximum endothermic peak is denoted as Tm (°C) and the peak temperature of the maximum exothermic peak is denoted as Tc (°C), Tc is 5°C or more lower than Tm. That is, Tm-Tc is 5°C or more.

[0028] Tm-Tc is preferably 5-20°C, more preferably 7-15°C, even more preferably 8-12°C, and even more preferably 9-11°C. As described above, when the release agent or hydrocarbon wax melts, it becomes compatible with the organosilicon polymer shell, causing a freezing point depression and resulting in a Tm-Tc of 5°C or higher. As a result, the shell softens, and the melted release agent or hydrocarbon wax can easily seep out from the parts where compatibility has progressed. Therefore, when the particles are used as an external additive for toner, the fixing and wrapping properties are improved.

[0029] Tm-Tc represents the compatibility between the crystalline material used for the core and the shell material, and can be controlled by the types of core and shell materials and the conditions for shell formation. For example, Tm-Tc can be increased by selecting materials with similar SP values. Conversely, Tm-Tc can be decreased by selecting materials with distant SP values. As shown in Patent Document 3, an organosilicon compound having a methacryloyl group in the shell is used When a silicon polymer is used, the compatibility with other materials decreases because vinyl polymerization bonds are added in addition to siloxane bonds, and the Tm-Tc is expected to be less than 5°C.

[0030] Tc is preferably 50 to 110°C, more preferably 55 to 100°C, even more preferably 60 to 90°C, and even more preferably 62 to 70°C.

[0031] The crystalline release agent contained in the core is not particularly limited, but the following are examples. The crystalline release agent is preferably at least one ester wax selected from the group consisting of ester waxes mainly composed of fatty acid esters such as carnauba wax, behenyl behenate, and dipentaerythritol stearate. The above waxes can be used individually or in combination of two or more. Furthermore, a mold release agent is defined as having a kinematic viscosity of 100 mm at 110°C. 2This refers to substances with a viscosity of less than / second. The kinematic viscosity at 110°C of a core containing a crystalline release agent or hydrocarbon wax is preferably 1 to 60 mm². 2 / second, more preferably 2-30mm 2 The value is / second, and more preferably 4-10mm 2 It is per second.

[0032] The hydrocarbon waxes contained in the core are not particularly limited, but the following are examples: The hydrocarbon wax is preferably at least one hydrocarbon wax selected from the group consisting of low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, and paraffin wax. The above waxes can be used individually or in combination of two or more. Hydrocarbon waxes preferably include paraffin wax.

[0033] By using crystalline release agents or hydrocarbon waxes in the core, fixing and wrapping can be suppressed when used as an external additive for toner. Furthermore, compared to cases where resins such as styrene-acrylic resin are used in the core, the amount of release agent contained in the toner particles can be reduced, which is expected to improve durability and make it easier to suppress image streaks and fogging. In addition, the amount of release agent present on the surface of the toner matrix particles can be reduced, which is expected to improve charge rise performance.

[0034] Known methods can be used to atomize these release agents and hydrocarbon waxes. Examples include emulsification by stirring or ultrasound in the presence of a surfactant, phase inversion emulsification, emulsion polymerization, and emulsion aggregation.

[0035] The shell contains an organosilicon polymer. The organosilicon polymer improves durability when the particles are used as an external additive for toner, and suppresses image streaks and fogging. The shell does not necessarily have to cover the entire core; there may be portions of the core that are partially exposed, as long as this does not impair the effects of this disclosure. Specific examples of the organosilicon polymer contained in the shell include polymers of organosilicon compounds having a siloxane bond as the main chain. Known methods can be used to form the organosilicon polymer as the shell. For example, an organosilicon compound such as alkoxysilane is added to a solvent in which the core is dispersed, and hydrolysis and condensation are caused by controlling the temperature and pH to form the shell.

[0036] The organosilicon polymer is preferably a polycondensate of at least one organosilicon compound selected from the group consisting of organosilicon compounds having a structure represented by the following formula (Z).

Chemical formula

[0037] In formula (Z), R a represents an alkyl group or an aryl group (preferably a phenyl group) having 1 to 8 carbon atoms (preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2). Preferably, it is an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2). R 1 , R 2 and R 3 each independently represent a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2). R 1 , R 2 and R 3 are preferably each independently an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2). R 1 , R 2 and R 3 are reactive groups that undergo hydrolysis, addition polymerization, and condensation to form a crosslinked structure. Also, the hydrolysis, addition polymerization, and condensation of R1, R2, and R3 can be controlled by the reaction temperature, reaction time, reaction solvent, and pH.

[0038] For organosilicon compounds, it is preferable to use alkoxysilanes. Examples of alkoxysilanes include the following: Compounds containing two alkoxy groups; dimethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane Compounds containing three alkoxy groups: methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane A compound having four alkoxy groups; tetramethoxysilane

[0039] Among the above, the organosilicon polymer is preferably a condensed polymer of at least one organosilicon compound selected from the group consisting of alkoxysilanes having three alkoxy groups. The organosilicon polymer is preferably a condensed polymer of at least one organosilicon compound selected from the group consisting of, for example, methyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and octyltriethoxysilane. Furthermore, two or more types of alkoxysilanes may be used in combination. In this case, those with one alkoxy group can also be used. Examples are given below. Compounds containing one alkoxy group; trimethylmethoxysilane, triethylmethoxysilane

[0040] In particular, it is preferable that the organosilicon polymer contains a T3 unit structure represented by the following formula (RT3). Including the RT3 structure makes it easier to suppress fogging after durable use. R-SiO 3 / 2 ...(RT3) In formula (RT3), R represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2 carbon atoms).

[0041] Organosilicon polymers having the structure (RT3) can be obtained, for example, by hydrolysis and condensation of a compound appropriately selected from organosilicon compounds having the structure represented by the above formula (Z). Preferably, it is a condensed polymer of an alkoxysilane having three alkoxy groups. In this structure, R is an alkyl group having 1 to 6 carbon atoms, and R in formula (Z) a This corresponds to the following. Examples of alkoxysilanes having three alkoxy groups are listed below. These may be used individually or in combination of two or more types. The organosilicon polymer is preferably a condensed polymer of at least one selected from the group consisting of methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, and hexyltrimethoxysilane. More preferably, it is a condensed polymer of methyltrimethoxysilane.

[0042] The reason why the presence of the structure represented by (RT3) makes it easier to suppress clouding after durable use is thought to be because the steric hindrance is reduced when the alkoxy group condenses, and a strong shell is formed, thereby suppressing deformation of the external additive.

[0043] Solids of organosilicon polymers 29 In Si-NMR measurement, RT3 is defined as the area of ​​the peak corresponding to the structure represented by (RT3), and S is the sum of the peak areas in M, D, T, and Q units. The ratio of RT3 to S (RT3 / S) is preferably 0.50 to 1.00, more preferably 0.80 to 1.00, and even more preferably 0.90 to 1.00. Within this range, it indicates that the organosilicon polymer sufficiently contains the structure represented by (RT3), further improving the effectiveness and durability of the mold release agent.

[0044] Tm is preferably 60 to 120°C, more preferably 65 to 100°C, even more preferably 70 to 90°C, and even more preferably 72 to 80°C. Furthermore, Tm is more preferably 100°C or lower. That is, it is preferable that the melting point of the crystalline release agent or hydrocarbon wax contained in the core is 100°C or lower. When core-shell type particles are used as an external additive for toner, a Tm of 100°C or less allows the core to easily microcrystallize when the prepared external additive is heated (distilled) and cooled while dispersed in an aqueous solution, thereby improving the durability of the external additive. In other words, it is thought that the core melted by heating (distillation) becomes compatible with a portion of the shell, and when this solidifies, the compatible shell components become crystal nuclei, causing the core to become polycrystalline. The grain boundaries then disperse external stress, making it more resistant to deformation. This can further suppress image quality degradation such as development streaks after prolonged use.

[0045] Core-shell type particles may be surface-treated with silane coupling agents, titanium coupling agents, higher fatty acids, silicone oils, silicone varnishes, various modified silicone varnishes, etc. Surface treatment agents may be used alone or in combination of two or more. This allows for adjustment of the charge level of external additives, improvement of heat resistance during storage, and improvement of environmental stability.

[0046] Next, I will explain toner. The toner comprises toner particles having a binder resin and an external additive, wherein the external additive is the core-shell type particle described above.

[0047] This configuration allows for the creation of toner that achieves both high speed and long lifespan. Specifically, because the release agent or hydrocarbon wax can seep out to the outside even under lighter pressure during fixing, good release properties can be maintained even as speeds increase, while achieving a longer lifespan by reducing the total content of the release agent or hydrocarbon wax.

[0048] The following describes the preferred form of toner. Note that the toner described here is not limited to what is stated below. First, let's discuss external additives. The external additives used in toners are the core-shell type particles described above. Furthermore, particles other than core-shell type particles may be used in combination as external additives if necessary. This allows for control over properties such as fluidity, electrostatic charge, and cleaning ability.

[0049] Other external additives that can be used in combination include, for example, inorganic oxide microparticles consisting of silica microparticles, alumina microparticles, titanium oxide microparticles, inorganic stearic acid compound microparticles such as aluminum stearate microparticles and zinc stearate microparticles, or inorganic titanate compound microparticles such as strontium titanate and zinc titanate. These external additives can be used individually or in combination of two or more.

[0050] The total amount of these external additives added is preferably 0.05 parts by mass or more and 10.00 parts by mass or less, and more preferably 0.1 parts by mass or more and 5.0 parts by mass or less, per 100 parts by mass of toner particles.

[0051] Known methods can be used to fix external additives to the surface of toner particles. For example, fixation using a Henschel mixer (dry method) or fixation by dispersing the toner particles and external additives in a solvent and then agglomerating them (wet method) can be used.

[0052] External addition is preferably done by a wet method. For example, a dispersion is prepared in which toner particles and core-shell type particles as an external additive are dispersed in an aqueous medium. If necessary, the dispersion is heated to 40-70°C (preferably 50-60°C). The pH of the dispersion is adjusted to 4.0-7.0 (preferably 5.0-6.0). The dispersion is heated to 80-120°C (preferably 90-110°C) (distillation), held for 5-200 minutes (preferably 30-90 minutes), and then cooled (e.g., air-cooled) to obtain toner.

[0053] Next, we will discuss the binder resin. The toner particles contain a binder resin. The binder resin is not particularly limited, and any known type can be used. For example, monopolymers of aromatic vinyl compounds such as polystyrene and polyvinyltoluene and their substituted products; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, Copolymers of aromatic vinyl compounds such as ethylene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer; monopolymers of aliphatic vinyl compounds such as polyethylene and polypropylene and their substituted derivatives; vinyl resins such as polyvinyl acetate, polyvinyl polypropionate, polyvinyl benzoate, polyvinyl butyrate, polyvinyl benzoate, polyvinyl formate, and polyvinyl butyral; vinyl ether resins; vinyl ketone resins; acrylic polymers; methacrylic polymers; silicone resins; polyester resins; polyamide resins; epoxy resins; phenolic resins; rosin, modified rosin, and terpene resins. These can be used individually or in combination.

[0054] The binder resins include aromatic vinyl compounds such as styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, and styrene-methacrylate copolymer. It is preferable that the material contains styrene-acrylic resins such as ethyl acrylate copolymer and styrene-butyl methacrylate copolymer.

[0055] Examples of aromatic vinyl compounds and their substituted derivatives include the following: Examples of styrene or styrene derivatives include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene.

[0056] Examples of polymerizable monomers that form acrylic polymers include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate.

[0057] Examples of polymerizable monomers that form methacrylic polymers include methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate.

[0058] As the polyester resin, a condensation polymer of the following carboxylic acid component and alcohol component can be used. Examples of carboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of alcohol components include bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

[0059] Furthermore, the polyester resin may be a polyester resin containing urea groups. It is preferable that the carboxyl groups at the ends of the polyester resin are not capped. A silicon-containing polyester resin may be used as the polyester resin. Preferably, the toner particles contain a silicon-containing polyester resin. This allows for the detection of carbon atoms and silicon atoms when time-of-flight secondary ion mass spectrometry is performed on the surface of the toner particles.

[0060] Silicon-containing polyester resins include resins in which a silane compound is bonded to a polyester resin. For example, it is preferable that the resin has an aminosilane bonded (e.g., an amide bond) to the carboxyl group of the polyester resin. As the aminosilane, known compounds such as 3-aminopropyltrimethoxysilane can be used. In silicon-containing polyester resins, the silicon concentration is preferably 0.05 to 0.50% by mass, and more preferably 0.10 to 0.30% by mass.

[0061] When polyester resin is used as the binder resin, the content of polyester resin in the binder resin The proportion is preferably 1.0 to 15.0% by mass, and more preferably 2.0 to 10.0% by mass. The content of silicon-containing polyester resin in the binder resin is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 3.0% by mass, and even more preferably 0.5 to 1.5% by mass. The weight-average molecular weight Mw of the polyester resin is not particularly limited, but is preferably 5000 to 50000, and more preferably 8000 to 30000.

[0062] The binder resin may have polymerizable functional groups in order to improve the viscosity change of the toner at high temperatures. Examples of polymerizable functional groups include vinyl groups, isocyanate groups, epoxy groups, amino groups, carboxyl groups, and hydroxyl groups.

[0063] Among these, styrene-acrylic resins, particularly styrene-butyl acrylate, are preferred in terms of developing properties and fixing properties. The method for producing the polymer is not particularly limited, and known methods can be used. The content of styrene-acrylic resin in the binder resin is preferably 50 to 100% by mass, more preferably 80 to 98% by mass, and even more preferably 90 to 95% by mass.

[0064] Next, I will discuss wax. The toner particles may contain wax as needed. Adding wax can further improve mold release properties. Additionally, softening the toner particles can improve low-temperature adhesion. However, since the external additive provides mold release properties, the toner particles do not necessarily need to contain wax. The wax is not particularly limited and includes the following: Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax, and deoxidized fatty acid esters such as deoxidized carnauba wax, which are partially or completely deoxidized; saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bis-ste Examples include saturated fatty acid bisamides such as acidamide, ethylene biscaprate, ethylene bislaurate, and hexamethylene bisstearate; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'dioleyl adipamide, and N,N'dioleyl sebacinamide; aromatic bisamides such as m-xylene bisstearate and N,N'distearyl isophthalamide; fatty acid metal salts (generally known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; 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. The above waxes can be used individually or in combination of two or more.

[0065] Examples of aliphatic alcohols that form ester waxes include 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, undecyl alcohol, lauryl alcohol, myristyl alcohol, 1-hexadecanol, and stearyl alcohol. Examples include alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol. Examples of aliphatic carboxylic acids include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. The wax content is preferably 0.5 parts by mass or more and 30.0 parts by mass or less per 100.0 parts by mass of the binder resin or polymerizable monomer.

[0066] Next, we will discuss colorants. The toner particles may contain a colorant as needed. The colorant is not particularly limited, and known colorants such as those listed below can be used. Yellow pigments used include condensed azo compounds such as yellow iron oxide, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Hansa Yellow 10G, benzidine Yellow G, benzidine Yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake, as well as isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following can be mentioned. CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180. Examples of orange pigments include the following: Permanent Orange GTR, Pyrazolon Orange, Balkan Orange, Benzidine Orange G, Induthrene Brilliant Orange RK, Induthrene Brilliant Orange GK.

[0067] Examples of red pigments include condensed azo compounds such as red iron oxide, permanent red 4R, lysol red, pyrazolone red, watching red calcium salt, lake red C, lake red D, brilliant carmine 6B, brilliant carmine 3B, eoxin lake, rhodamine lake B, and alizarin lake, as well as diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following can be mentioned. CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254. Examples of blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, copper phthalocyanine compounds and their derivatives such as induthlene blue BG, anthraquinone compounds, and basic dye lake compounds. Specifically, the following are examples: CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66.

[0068] Examples of purple pigments include Fast Violet B and Methyl Violet Lake. Examples of green pigments include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of white pigments include zinc oxide, titanium dioxide, antimony white, and zinc sulfide. Examples of black pigments include carbon black, aniline black, non-magnetic ferrite, magnetite, and pigments colored black using the above-mentioned yellow, red, and blue colorants. These colorants can be used individually, in combination, or even in solid solution form. It is possible. If necessary, the surface of the colorant may be treated with a substance that does not inhibit polymerization. Furthermore, the colorant content is preferably 1.0 part by mass or more and 15.0 parts by mass or less per 100.0 parts by mass of the binder resin or polymerizable monomer.

[0069] Next, we will discuss charge control agents. Toner particles may contain a charge control agent as needed. While known charge control agents can be used, a charge control agent that has a fast triboelectric charging rate and can stably maintain a constant triboelectric charge is preferred. Furthermore, when toner particles are manufactured by polymerization, a charge control agent with low polymerization inhibitory properties and substantially no solubilizes in aqueous media is preferred. Charge control agents include those that control the toner's charge to match the load charge and those that control its charge to match the positive charge. Examples of devices that control toner according to load voltage include the following: Examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acid and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, and resin-based charge control agents.

[0070] On the other hand, examples of devices that control the toner to be positively charged include the following: Examples of lake pigments include nigrosine and nigrosine-modified products such as fatty acid metal salts, guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof, as well as lake pigments made from these, triphenylmethane dyes and lake pigments made from these (lakening agents include phosphotungstic acid, phosphomolybdic acid, phosphotungstenmolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids, and resin-based charge control agents. Charge control agents can be used alone or in combination of two or more types. Among these charge control agents, metal-containing salicylic acid compounds are preferred, and those in which the metal is aluminum or zirconium are particularly preferred. The amount of charge control agent added is preferably 0.1 parts by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the binder resin, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less.

[0071] Furthermore, as the charge-controlled resin, it is preferable to use a polymer or copolymer having a sulfonic acid group, a sulfonic acid base, or a sulfonic acid ester group. As the polymer having a sulfonic acid group, a sulfonic acid base, or a sulfonic acid ester group, it is particularly preferable to contain 2% by mass or more of a sulfonic acid group-containing acrylamide monomer or a sulfonic acid group-containing methacrylamide monomer in copolymerization ratio. More preferably, it contains 5% by mass or more in copolymerization ratio. The charge-controlled resin preferably has a glass transition temperature (Tg) of 35°C to 90°C. Furthermore, it is preferable that the peak molecular weight (Mp) is between 10,000 and 30,000, and the weight-average molecular weight (Mw) is between 25,000 and 50,000. Using this charge-controlled resin allows for the imparting of desirable triboelectric properties without affecting the thermal properties required for toner particles. Moreover, because the charge-controlled resin contains sulfonic acid groups, the dispersibility of the charge-controlled resin itself and the dispersibility of the colorant in the colorant dispersion is improved, further enhancing coloring power, transparency, and triboelectric properties.

[0072] Next, we will discuss the toner manufacturing method. Methods for producing toner particles can be known. Examples include dry methods such as kneading and grinding; and wet methods such as suspension polymerization, dissolution and suspension, emulsification and agglutination, and emulsification polymerization and agglutination. In particular, wet methods are preferred from the viewpoint of sharpening the particle size distribution of toner particles, improving the average circularity of toner particles, and forming a core-shell structure.

[0073] For example, when manufacturing toner particles using a dry manufacturing method called the kneading and grinding method, the binder resin and, if necessary, wax, colorants, charge control agents, and other additives are thoroughly mixed using a mixer such as a Henschel mixer or ball mill. Then, the various materials are dispersed or dissolved by melt kneading using a hot kneader such as a heated roll, kneader, or extruder, and toner particles are obtained through a cooling and solidification process, a grinding process, a classification process, and, if necessary, a surface treatment process. In the grinding process, known grinding devices such as mechanical impact type and jet type may be used. The order of the classification process and the surface treatment process does not matter. For production efficiency, it is preferable to use a multi-segment classifier in the classification process.

[0074] Next, we will discuss the case of manufacturing toner particles using the suspension polymerization method, which is a wet manufacturing method. The following describes, but is not limited to, an example of toner particle production using suspension polymerization. In the suspension polymerization method, first, polymerizable monomers for generating a binder resin, along with wax, colorants, charge control agents, crosslinking agents, polymerization initiators, and other additives as needed, are uniformly dissolved or dispersed using a disperser such as a ball mill or ultrasonic disperser to obtain a polymerizable monomer composition. (Preparation step of polymerizable monomer composition) Examples of the polymerizable monomers include those exemplified as polymerizable monomers that form the vinyl copolymers mentioned above.

[0075] The above-mentioned crosslinking agent is added as needed during the polymerization of polymerizable monomers to control the molecular weight of the binder resin. The crosslinking agent mainly consists of compounds having two or more polymerizable double bonds. Examples include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol #200, #400, and #600 diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and carboxylic acid esters having two double bonds, such as those obtained by replacing the above acrylates with methacrylate, as well as divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone, and compounds having three or more vinyl groups. These can be used individually or as mixtures of two or more. The amount of the above-mentioned crosslinking agent added is preferably 0.1 parts by mass or more and 15.0 parts by mass per 100 parts by mass of polymerizable monomer.

[0076] Next, the polymerizable monomer composition is added to a pre-prepared aqueous medium, and droplets of the polymerizable monomer composition are formed to the desired toner particle size using a stirrer or disperser with high shear force (granulation step). In the granulation process, it is preferable for the aqueous medium to contain a dispersion stabilizer in order to control the particle size of toner particles, sharpen the particle size distribution, and suppress the aggregation of toner particles during the manufacturing process. Dispersion stabilizers are generally broadly classified into polymers that exhibit repulsive force due to steric hindrance and poorly water-soluble inorganic compounds that stabilize dispersion through electrostatic repulsion. Since the fine particles dissolve in acids and alkalis, they can be easily removed by washing with an acid or alkali after polymerization, making them suitable for use. For dispersion stabilizers of poorly water-soluble inorganic compounds, those containing magnesium, calcium, barium, zinc, aluminum, or phosphorus are preferably used. More preferably, those containing magnesium, calcium, aluminum, or phosphorus are desired. Specifically, the following are examples.

[0077] Magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, hydroxyapatide. When using these poorly water-soluble inorganic dispersants, they may be used as is, but to obtain finer particles, the inorganic dispersant particles can be generated in an aqueous medium before use. For example, in the case of tricalcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed under high-speed stirring to generate water-insoluble calcium phosphate, enabling a more uniform and finer dispersion.

[0078] Organic compounds, such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, and starch, may be used in combination as dispersion stabilizers. It is preferable to use these dispersion stabilizers in an amount of 0.1 parts by mass to 20.0 parts by mass per 100 parts by mass of polymerizable monomer. Furthermore, in order to further refine these dispersion stabilizers, a surfactant may be added in an amount of 0.1 to 10.0 parts by mass per 100 parts by mass of polymerizable monomer. Specifically, commercially available nonionic, anionic, and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium lauryl sulfate, potassium stearate, and calcium oleate are preferably used.

[0079] After the granulation process, or while the granulation process is being carried out, the polymerizable monomers contained in the polymerizable monomer composition are polymerized at a temperature preferably set to 50°C or higher and 90°C or lower to obtain a toner particle dispersion (polymerization process). During the polymerization process, it is preferable to stir the mixture to ensure a uniform temperature distribution within the container. When adding a polymerization initiator, this can be done at any time and for any duration. Furthermore, the temperature may be increased in the latter half of the polymerization reaction to obtain a desired molecular weight distribution. Additionally, to remove unreacted polymerizable monomers, by-products, etc., some of the aqueous medium may be removed by distillation in the latter half of the reaction or after the reaction is complete. Distillation can be carried out under atmospheric pressure or reduced pressure.

[0080] In suspension polymerization, polymerization initiators with a half-life of 0.5 hours or more and 30 hours or less during the polymerization reaction are preferred. Furthermore, when the polymerization reaction is carried out using an amount of 0.5 parts by mass or more and 20 parts by mass or less per 100 parts by mass of polymerizable monomer, a polymer having a maximum molecular weight between 5000 and 50000 can be obtained. Oil-soluble initiators are generally used as polymerization initiators. Examples include the following:

[0081] Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, tert-butylperoxy Examples of peroxide initiators include sobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxypivalate, and cumene hydroperoxide.

[0082] Polymerization initiators may be used in combination with water-soluble initiators as needed, including the following: Ammonium persulfate, potassium persulfate, 2,2'-azobis(N,N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis(2-aminodinopropane) hydrochloride, azobis(isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate, or hydrogen peroxide. These polymerization initiators can be used individually or in combination, and chain transfer agents, polymerization inhibitors, etc., can be further added to control the degree of polymerization of the polymerizable monomers.

[0083] From the viewpoint of obtaining high-definition and high-resolution images, the weight-average particle size of the toner particles is preferably 3.0 μm to 10.0 μm. The weight-average particle size of the toner particles can be measured by the pore electrical resistance method. For example, it can be measured using the "Coulter Counter Multisizer 3" (manufactured by Beckman Coulter, Inc.). The toner particle dispersion obtained through the polymerization process is sent to a filtration process to separate the toner particles from the aqueous medium into solid and liquid components.

[0084] Solid-liquid separation to obtain toner particles from the resulting toner particle dispersion can be performed using a general filtration method. Subsequently, it is preferable to further wash the toner particles by rinsing with a reslurry or washing water to remove any remaining foreign matter from the surface of the toner particles. After thorough washing, solid-liquid separation is performed again to obtain a toner cake. Then, it is dried by known drying methods, and if necessary, particles with non-standard particle sizes are separated by classification to obtain toner particles. The separated particles with non-standard particle sizes may be reused to improve the final yield.

[0085] Furthermore, it is preferable that carbon atoms and silicon atoms are detected when time-of-flight secondary ion mass spectrometry is performed on the surface of the toner particles. This configuration can further improve the charge rise speed. This is thought to be because, when core-shell type particles used as an external additive become charged, the charge easily transfers from the carbon and silicon atoms constituting the organosilicon polymer contained in the shell of the external additive to the carbon and silicon atoms present on the surface of the toner particles. This effect is particularly pronounced when both carbon and silicon atoms are present in the region involved in charging. As a result of this charge diffusion, the region that can participate in charging increases, making charging easier. Consequently, the rate of charge build-up also improves.

[0086] To ensure that carbon atoms and silicon atoms are detectable on the surface of toner particles, one method is to use the silicon-containing polyester resin described above during the manufacturing of toner particles. Alternatively, during the manufacturing of toner particles, a condensate of an organosilicon compound having the structure represented by formula (Z) described above can be formed on the surface of the toner particles. In other words, it is preferable for the toner particles to have a condensate of an organosilicon compound on their surface. For example, a shell of an organosilicon compound condensate (organosilicon polymer) may be formed on the surface of the toner particles.

[0087] Next, let's discuss the developer. Toner can be used as a magnetic or non-magnetic one-component developer, or it may be mixed with a carrier to be used as a two-component developer. As carriers, magnetic particles made of known materials such as metals like iron, ferrite, and magnetite, or alloys of these metals with metals like aluminum and lead, can be used. Yes, it is possible. Among these, ferrite particles are preferred. In addition, as carriers, coated carriers in which the surface of magnetic particles is coated with a coating agent such as resin, or resin-dispersed carriers in which fine magnetic powder is dispersed in a binder resin may be used. The carrier material is preferably one with a volume-average particle size of 15 μm to 100 μm, and more preferably one with a particle size of 25 μm to 80 μm.

[0088] The following describes methods for measuring the various physical properties of core-shell type particles (external additives), etc. <Method for measuring the maximum ferret diameter of external additives> The maximum ferret diameter of the external additive is measured using a scanning electron microscope (Zeiss UltraPlus) and image measurement. The image acquisition conditions are as follows: (1) Sample preparation Carbon tape is attached to the sample stage (aluminum sample stage: 12.5 mm diameter x 6 mm), and the external additive for measuring the maximum ferret diameter, or the toner to which it is added, is placed on top of it. Further air blowing is used to remove excess sample from the sample stage. The sample stage is then set in the sample holder and placed in the electron microscope.

[0089] (2) Setting of electron microscope observation conditions The coverage rate of the external additive at the maximum ferret diameter is calculated using images obtained from backscattered electron imaging with Ultra Plus. In backscattered electron images, carbon tape and toner particles are observed at low brightness, while the external additive is observed at high brightness, making image processing easier. The acceleration voltage is set to 0.7kV and the working width (WD) to 3.0mm.

[0090] (3) Focus adjustment Set the observation magnification to 30000 (30k)x and adjust the Alignment and Stigma. Focus the external additive at an observation magnification of 50k. Note that if the tilt angle of the observation surface is large, it will be difficult to focus on the entire field of view simultaneously. When adjusting the focus, set the observation position so that the entire observation surface is in focus at the same time.

[0091] (4) Save the image Adjust the contrast and brightness as needed, and take a photograph at a size of 1024 x 768 pixels and save it. Take at least 10 of these images.

[0092] (5) Image analysis The maximum Ferret diameter is determined from the obtained SEM images using the image analysis software ImageJ (developed by Wayne Rasband). The calculation procedure is as follows. A) Set the scale using [Analyze]-[Set Scale]. B) Use [Process]-[Noise]-[Despeckle] to blur everything except the outline. C) Use [Process]-[Sharpen] to sharpen the outline. D) Set a threshold in [Image]-[Adjust]-[Threshold] and perform binarization. (Set the threshold to a value that leaves no noise but retains the external additive being measured (specifically, Auto)). E) Add the perimeter using [Process]-[Binary]-[Dilate] F) Use [Process]-[Binary]-[Erode] to erase the outer perimeter. G) Separate the overlaps using [Process]-[Binary]-[Watershed]. H) Eliminate all external additives except those to be evaluated. I) In [Analyze]-[Set Measurements], check [Ferets Diameter]. Also, set [Redirect to] to [None] and [Decimal Place (0-9)] to 3. J) Run the analysis using [Analyze]-[Analyze Particle]. K) Perform the same analysis on the remaining 9 observed images. L) The maximum Ferret diameter is defined as the (number mean + standard deviation) of the Ferret diameters obtained from the analysis results.

[0093] <Confirmation of core-shell structure of external additives> To confirm whether an external additive has a core-shell structure, TEM-EDX observation (energy-dispersive X-ray analysis using a transmission electron microscope) is used. For TEM observation, if an external additive is used, the sample is prepared by spraying the external additive onto a support film-attached grid and lightly blowing air through it before measurement. If the additive is externally added to the toner, cross-sectional observation is performed. The toner particle cross-section is prepared as follows.

[0094] Using an osmium plasma coater (filgen, OPC80T), an Os film (5nm) and a naphthalene film (20nm) are applied to the toner as protective films. After embedding in photocurable resin D800 (JEOL), a cross-section of toner particles with a thickness of 100nm is prepared using an ultrasonic ultramicrotome (Leica, UC7) at a cutting speed of 1mm / s. The obtained cross-sections are observed using the STEM function of TEM-EDX (TEM: JEOL, JEM2800 (200keV), EDX detector: JEOL, dry SD 100GV, EDX system: Thermo Fisher, NORAN SYSTEM7). The STEM probe size is adjusted to 1.0 nm, the observation magnification to 50-150 kHz, the EDX image size to 256 × 256 pixels, and the storage rate to 10,000 cps. 100 frames are then integrated to acquire the image.

[0095] If an external additive has a core-shell structure, silicon is abundant around the additive, while carbon is abundant inside the additive. The core-shell structure of the external additive can be confirmed by this and by observing the backscattered electron image using a method for measuring the maximum Ferret diameter of the external additive. Specifically, if the backscattered electron image shows no contrast originating from organic matter on the surface and is covered with contrast originating from silicon, then it can be determined that the external additive has a core-shell structure.

[0096] <Structural evaluation of organosilicon polymer shells> NMR is used to confirm that the organosilicon polymer shell of the external additive has the structure represented by (RT3). If isolated external additives are available, perform the measurement directly. If the external additives are fixed to the toner, extract the organosilicon polymer shell as follows. Dissolve 1 g of toner in 31 g of chloroform in a vial and disperse. Prepare the dispersion by treating it with an ultrasonic homogenizer for 30 minutes. Ultrasonic processing equipment: Ultrasonic homogenizer VP-050 (manufactured by Taitec Co., Ltd.) Microchip: Stepped microchip, tip diameter φ2mm Microchip tip position: Center of the glass vial, 5mm above the bottom of the vial. Ultrasonic conditions: Intensity 30%, 30 minutes. During this time, apply ultrasound while cooling the vial with ice water to prevent the dispersion from rising in temperature.

[0097] The dispersion was transferred to a 50 mL glass tube for the swing rotor and centrifuged in a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) at 58.33S. -1 Then, centrifugation is performed for 30 minutes. After centrifugation, the organosilicon polymer shells are separated into layers within the glass tube. When multiple external additive components are present, each layer is separated by component and observed using SEM-EDX to identify the layer containing the organosilicon polymer shell based on its shell structure and Si,O elemental composition. This is extracted and dispersed again in 10 g of chloroform for washing, and the organosilicon polymer shell is separated using a centrifuge. After further washing, the extracted organosilicon polymer shell is vacuum-dried (40°C / 24 hours) to remove the chloroform and isolate the organosilicon polymer shell.

[0098] The structure of the organosilicon polymer shell was evaluated using the isolated sample described above. 29 Measurement is performed using Si-NMR. solid 29 In Si-NMR, peaks are detected in different shift regions depending on the number of functional groups bonded to the Si that constitutes the organosilicon polymer shell. The number of functional groups in each peak can be determined using standard samples. Furthermore, the relative abundance of each constituent compound can be calculated from the obtained peak areas. Since the (RT3) structure has only one functional group bonded to Si, it is sufficient to detect the peak corresponding to this. solid 29 The measurement conditions for Si-NMR are as follows, for example: Equipment: JEOLRESONANCE JNM-ECX500II Measurement temperature: room temperature Measurement method: DDMAS method 29 Si 45° Sample tube: Zirconia 3.2mmφ Sample: Filled in a test tube in powder form. Sample rotation speed: 10kHz Relaxation delay: 180s Total number of times: 2000

[0099] To determine the proportion of the present Si that has an RT3 structure (RT3 / S), after the measurement, the peaks of multiple silane components with different substituents and bonding groups of the organosilicon polymer shell are separated by curve fitting, and the peak area of ​​each is calculated. Specifically, the peaks are separated into the following M, D, T, and Q units using curve fitting. Curve fitting is performed using EXcalibur for Windows® version 4.2 (EX series), software for the JNM-EX400 manufactured by JEOL Ltd. The measurement data is loaded by clicking "1D Pro" from the menu icon. Next, "Curve fitting function" is selected from "Command" in the menu bar to perform curve fitting. Curve fitting is performed for each component so that the difference between the composite peak (the summation of each peak obtained by curve fitting) and the peak in the measurement result (composite peak difference) is minimized. The RT3 structure is included in the following T units. M unit: (R i )(R j)(R k )SiO 1 / 2 Formula (4) D unit: (R g )(R h )Si(O 1 / 2 )2 formula (5) T unit: R m si(O 1 / 2 )3 formula (6) Q unit: Si(O) 1 / 2 )4 formula (7) R in equations (4), (5), and (6) i , R j , R k , R g , R h , R m This refers to an alkyl group, halogen atom, hydroxyl group, acetoxy group, or alkoxy group, such as a hydrocarbon group having 1 to 6 carbon atoms, that is bonded to silicon. After peak separation, calculate the sum S of all integral values ​​in units of M, D, T, and Q.

[0100] Furthermore, the identification of R in the (RT3) structure is solid 13 This is performed by 13C-NMR. solid 13 The measurement conditions for 1C-NMR are as follows, for example: Equipment: JEOLRESONANCE JNM-ECX500II Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 123.25MHz ( 13 C) Sample tube: Zirconia 3.2mmφ Sample: Filled in a test tube in powder form. Sample rotation speed: 20kHz Reference substance: Adamantane (external standard: 29.5ppm) Contact time: 2ms Delay time: 2 seconds Total number of times: 1024 In this method, the methyl group (Si-CH3), ethyl group (Si-C2H5), propyl group (Si-C3H7), butyl group (Si-C4H9), and pentyl group (Si-C5H) bonded to the silicon atom are obtained. 11), hexyl group (Si-C6H 13 The above R is confirmed by the presence or absence of a signal caused by ) or a phenyl group (Si-C6H5), etc. Based on the above analysis, the area of ​​the peak corresponding to the structure represented by (RT3) is defined as RT3, and RT3 / S is calculated.

[0101] <Measurement of maximum endothermic peak Tm and maximum exothermic peak Tc of external additives> A differential scanning calorimetry analyzer is used to measure the maximum endothermic peak Tm and maximum exothermic peak Tc of the external additive. If isolated external additives are available, perform the measurement directly. If the external additives are fixed to the toner, remove them as follows. Weigh 20g of "Contaminon N" (a 10% aqueous solution of pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder) into a 50mL vial and mix with 1g of toner. Next, place it in an Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX) and shake for 120 seconds at a speed of 50. This will cause the external additive to migrate from the surface of the toner particles to the dispersion. Subsequently, a centrifugal separator (H-9R; manufactured by Kokusan Co., Ltd.) (16.67S) -1 (5 minutes) The toner particles and the external additives that have migrated to the supernatant are separated. The supernatant containing the external additives is separated and further processed at 58.33S -1 Then, centrifugation is performed under conditions of 30 minutes. After centrifugation, the core-shell type external additive is separated into layers in the glass tube. If multiple external additive components are present, each separated layer is observed by SEM-EDX, and the layer containing the core-shell type external additive is identified from the shell structure and the elemental composition of Si and O. This is extracted, dispersed in 10 g of deionized water for washing, and the core-shell type external additive is separated using a centrifuge.

[0102] The isolated external additives are measured using a differential scanning calorimetry analyzer "Q2000" (TA Instruments) in accordance with ASTM D3418-82. The temperature correction for the instrument's detection unit uses the melting points of indium and zinc, and the heat of fusion of indium is used for heat quantity correction. Specifically, 2 mg of the sample is accurately weighed and placed in an aluminum pan. An empty aluminum pan is used as a reference, and measurements are taken within the measurement temperature range of 30 to 120°C at a heating rate of 10.0°C / min. During the measurement, the temperature is first raised to 120°C, and then cooled to 30°C at a cooling rate of 10.0°C / min. In the DSC curve obtained during the heating process, the temperature indicated by the maximum endothermic peak is defined as Tm (°C), and in the DSC curve obtained during the cooling process, the temperature indicated by the maximum exothermic peak is defined as Tc (°C).

[0103] <Structural evaluation of the core> Pyrolysis GC-MS is used to evaluate the core structure of external additives. If isolated external additives are available, perform the measurements directly. If the external additives are fixed to the toner, extract them using the method described above when measuring Tm and Tc.

[0104] For isolated external additives, pyrolysis GC / MS was performed to determine whether they were crystalline release agents or carbon This method enables structural evaluation of cores containing hydrochloric wax. By analyzing the mass spectrum of components of crystalline release agents or hydrocarbon wax-derived decomposition products generated when external additives are thermally decomposed at approximately 550°C to 700°C, the core structure can be identified. The equipment and measurement conditions are shown below. Crystallinity can be confirmed by evaluating the above-mentioned Tm and Tc. • Pyrolysis apparatus: JPS-700 (manufactured by Nippon Analytical Industry Co., Ltd.) ·Decomposition temperature: 590℃ • GC / MS system: Focus GC / ISQ (Thermo Fisher) • Column: HP-5MS, length 60m, inner diameter 0.25mm, film thickness 0.25μm ·Inlet temperature: 200℃ Flow pressure: 100kPa • Split: 50 mL / min • MS ionization: EI • Ion source temperature: 200℃ Mass Range: 45-650

[0105] <Method for evaluating carbon atoms and silicon atoms on the surface of toner particles> The identification of carbon and silicon atoms present on the surface of toner particles is performed by evaluating the toner particles using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). The equipment and measurement conditions used are shown below. • Measurement device: nanoTOF II (product name, manufactured by ULVAC-FI, Inc.) • Primary ion species: Bi 3++ • Acceleration voltage: 30kV • Primary ion current: 0.05 pA • Repetition frequency: 8.2kHz • Raster Mode: Unbunch • Raster size: 50μm x 50μm, 256 x 256 pixels • Measurement mode: Positive • Neutralizing electron gun: Used • Measurement time: 600 seconds • Sample preparation: Toner is fixed to an indium sheet. • Sample pretreatment: None By using ULVAC-FI's standard software (TOF-DR) to image toner particles based on their carbon and silicon mass numbers, it is possible to confirm the presence of carbon and silicon atoms in the exposed regions of the toner particle surface. The selection of areas where the toner particle surface is exposed can be achieved by observing the area where the ion image was measured using SEM and comparing the images.

[0106] <Method for evaluating the kinematic viscosity of a core containing a release agent or wax> The kinematic viscosity of a core containing a release agent or wax should be measured if the core is available. If measuring from an external additive, the measurement should be performed on an extracted core. If an isolated external additive is available, it should be used for extraction. If the external additive is fixed to the toner, the Tm and Tc measurements should be performed after the external additive has been removed using the method described above.

[0107] Weigh 1 g of the external additive obtained as described above, place it in cylindrical filter paper (Toyo Filter Paper Co., Ltd. No. 84), and place it in a Soxhlet extractor. Extract using 200 mL of THF as the solvent for 20 hours, and the solid obtained by desolventing the extract is the core of the release agent or hydrocarbon wax. Repeat this process multiple times to obtain the required amount of core. For measuring kinematic viscosity, a fully automated micro-kinematic viscosity measurement system (manufactured by Viscotec Co., Ltd.) is used, and the kinematic viscosity at 110°C is measured.

[0108] <Method for extracting polyester resin from toner particles> The polyester resin in the toner particles is extracted using tetrahydrofuran (THF) and separated by solvent gradient elution. The preparation method is shown below. Weigh 10.0 g of toner particles and place them in cylindrical filter paper (Toyo Filter Paper Co., Ltd. No. 84) before placing them in a Soxhlet extractor. Extraction is carried out for 20 hours using 200 mL of THF as the solvent, and the solid obtained by desolventing the extract is the THF-soluble component. The THF-soluble component contains polyester resin. Repeat this process multiple times to obtain the required amount of THF-soluble component. For the solvent gradient elution method, a gradient preparative HPLC (Shimadzu LC-20AP high-pressure gradient preparative system, Waters SunFire preparative column 50 mm diameter, 250 mm length) is used. The column temperature is 30°C, the flow rate is 50 mL / min, and acetonitrile is used as the poor solvent and THF as the good solvent for the mobile phase. 0.02 g of THF-soluble fraction obtained by extraction is dissolved in 1.5 mL of THF to prepare the sample for separation. The mobile phase is started with a composition of 100% acetonitrile. Five minutes after sample injection, the proportion of THF is increased by 4% per minute until the mobile phase is composed of 100% THF over 25 minutes. The resulting fraction can be dried to separate the components. This allows for the acquisition of polyester resin. The specific components of the fraction that constitute the polyester resin will be described later. 13 This can be determined by 13C-NMR measurement.

[0109] <Method for calculating the percentage of ester bonds> The proportion of ester bonds in polyester resin is, 13 The calculation is performed using 1C-NMR as follows. The measurement conditions are as follows. Equipment: Bruker FT-NMR AVANCE-600 Sample quantity: 150 mg Measurement temperature: room temperature Measurement method: Decoupling method with reverse gate Solvent: Deuterated chloroform 0.75 ml Relaxation agent: Chromium(III) acetylacetonate Total number of times: 30,000 Quantitative analysis is performed using the internal standard method, utilizing the peak area appearing at 160.0–170.0 ppm, which is derived from ester bonds.

[0110] <Measurement of silicon concentration in silicon-containing polyester resin> The silicon atom content in polyester resin is determined using the wavelength-dispersive X-ray fluorescence analyzer "Axios" (PANalytical). Measurement conditions are set and the measurement data is analyzed using the included dedicated software "SuperQ ver.4.0F" (PANalytical). The anode of the X-ray tube will be Rh, and the acceleration voltage and current will be 24kV and 100mA, respectively. The measurement atmosphere is a vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. A proportional counter (PC) is used as the detector. The measurement is performed by measuring the count rate (unit: cps) of Si-Kα lines observed at the diffraction angle (2θ) = 109.08° when PET is used as the spectroscopic crystal, and calculating it using the calibration curve below. The measurement sample will be either the polyester resin itself or the polyester resin extracted from toner particles using the extraction method described above. The pellets used for measurement are manufactured using the "BRE-32" tablet molding and compression machine (Maekawa Testing Machine Co., Ltd.). 4g of the measurement sample is placed in a dedicated aluminum press ring, leveled, and pressurized at 20MPa for 60 seconds to form pellets with a thickness of 2mm and a diameter of 39mm. The binder [product name: Spectro Blend, composition: C 81.0, O 2.9, H 13.5, N 2.6 (mass%), chemical formula: C] is used as a pellet to create a calibration curve for determining the content. 19 H 38 ON, Form: Powder (44μm); Manufactured by Rigaku Corporation Add 0.5 parts by mass of SiO2 (hydrophobic fumed silica) [product name: AEROSIL NAX50, specific surface area: 40±10, carbon content: 0.45~0.85%; manufactured by Nippon Aerosil Co., Ltd.] to 100 parts by mass, mix thoroughly using a coffee mill, and prepare pelletized products. Similarly, prepare mixed and pelletized products with 5.0 parts by mass and 10.0 parts by mass of SiO2, respectively. A linear calibration curve is obtained by plotting the X-ray count rate on the vertical axis and the Si addition concentration in each calibration sample on the horizontal axis. Next, the counting rate of Si-Kα rays is measured in the same manner for the measurement sample. Then, the silicon atom content (mass %) is determined from the resulting calibration curve.

[0111] <Measurement of weight-average molecular weight (Mw) of resins such as polyester resin> The weight-average molecular weight (Mw) of polymers, resins, or toner particles is measured by gel permeation chromatography (GPC) as follows: First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the resulting solution is filtered through a solvent-resistant membrane filter, "Myshoridisk" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm, to obtain the sample solution. The sample solution is prepared so that the concentration of components soluble in THF is approximately 0.8% by mass. This sample solution is then used for measurement under the following conditions. Equipment: HLC8120 GPC (Detector: RI) (Manufactured by Tosoh Corporation) Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL / min Oven temperature: 40.0℃ Sample injection volume: 0.10 mL For calculating the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (product names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used. [Examples]

[0112] The present invention will be described in more detail below with reference to manufacturing examples and embodiments, but these are not intended to limit the present invention in any way. In the embodiments and comparative examples, all "parts" and "%" mentioned are on a mass basis unless otherwise specified.

[0113] <Preparation of external additive core 1> Preparation of the aqueous phase Pour 50.0 parts of deionized water into a No. 11 mayonnaise jar and dissolve 0.2 parts of sodium lauryl sulfate in it. Preparation of the oil phase 7.0 parts of toluene were used to dissolve 3.0 parts of HNP-9 (Nippon Seiro) as the core material. The oil phase was added to the stirred aqueous phase and dispersed using an ultrasonic homogenizer for 5 minutes (intermittent irradiation for 1 s, stop for 1 s). After desolvating the toluene with an evaporator, the excess sodium lauryl sulfate was removed using an ultrafiltration filter to obtain an aqueous dispersion of the external additive core 1. The maximum ferret diameter of the external additive core 1 was 110 nm, and the kinematic viscosity at 110°C was 7 mm². 2 It was per second.

[0114] <Preparation of external additive core 2> In a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube, 5.0 parts HNP-9 and 10.0 parts methyl ethyl ketone (MEK) were charged and heated to 50°C until dissolved. Then, 0.45 parts triethylamine was added while stirring. The crystalline material was thoroughly dissolved. After confirming that the mixture was dissolved, 40 parts of water were added dropwise at a rate of 2.5 parts / min to perform phase inversion emulsification, thereby obtaining a fine particle dispersion (solid content concentration 9.0% by mass). MEK was thoroughly removed by distillation using an evaporator at 60°C to obtain an aqueous dispersion of the external additive Core 2. The maximum ferret diameter of the external additive Core 2 was 12 nm, and the kinematic viscosity at 110°C was 7 mm². 2 It was per second.

[0115] <Preparation of external additive cores 3, 5-8, and 11> In the preparation of external additive core 1, aqueous dispersions of external additive cores 3, 5-8, and 11 were obtained in the same manner, except that the core material and dispersion time were changed as shown in Table 1. The maximum ferret diameter and kinematic viscosity at 110°C were as shown in Table 1. Note that Sazol C105 is a pentaerythritol stearate wax from Sazol Co., Ltd., and DP-18 is a pentaerythritol stearate wax from Nisshin Oillio Group Ltd.

[0116] <Preparation of external additive core 4> Preparation of the aqueous phase Pour 50.0 parts of deionized water into a No. 11 mayonnaise jar and dissolve 0.2 parts of sodium lauryl sulfate in it. Preparation of the oil phase 7.0 parts of toluene were dissolved in 3.0 parts of Sanwax 161-P (Sanyo Chemical Industries) as the core material. The oil phase was added to the stirred aqueous phase and dispersed for 5 minutes at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). After desolventing the toluene with an evaporator, the excess sodium lauryl sulfate was removed with an ultrafiltration filter to obtain an aqueous dispersion of the external additive core 4. The maximum ferret diameter of the external additive core 4 was 310 nm, and the kinematic viscosity at 110°C was 20 mm². 2 It was per second.

[0117] <Preparation of external additive core 9> In the preparation of external additive core 4, an aqueous dispersion of external additive core 9 was obtained in the same manner, except that the core material was changed as shown in Table 1. The maximum ferret diameter of external additive core 9 was 450 nm, and the kinematic viscosity at 110°C was 7 mm². 2 It was per second.

[0118] <Preparation of external additive core 10> In the preparation of external additive core 2, an aqueous dispersion of external additive core 10 was obtained in the same manner, except that the core material was changed to CW (Nisshin Oillio Group Ltd., behenyl behenate). The maximum ferret diameter of external additive core 10 was 50 nm, and the kinematic viscosity at 110°C was 48 mm². 2 It was per second.

[0119] <Preparation of external additive core 12> To an oil phase containing 78.0 parts styrene and 22.0 parts butyl acrylate, 150 parts of a 1.5% aqueous solution of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and dispersed. While stirring slowly for another 10 minutes, 0.3 parts potassium persulfate and 10.0 parts of deionized water were added. After nitrogen purging, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was complete, the reaction solution was cooled to room temperature, and deionized water was added to obtain an aqueous dispersion of the external additive Core 12 with a solid content of 12.5% ​​by mass. The maximum ferret diameter of the external additive Core 12 was 390 nm, and the kinematic viscosity at 110°C was 380 mm². 2 It was per second.

[0120] <Preparation of external additive core 13> In the preparation of external additive core 2, an aqueous dispersion of external additive core 13 was obtained in the same manner, except that the core material was changed as shown in Table 1. The maximum ferret diameter and kinematic viscosity at 110°C were as shown in Table 1.

[0121] <Preparation of external additive core 14> In the preparation of external additive core 4, an aqueous dispersion of external additive core 14 was obtained in the same manner, except that the core material and dispersion time were changed as shown in Table 1. The maximum ferret diameter and kinematic viscosity at 110°C are as shown in Table 1. It was a street.

[0122] <Preparation of external additive 1> First, the solid-liquid ratio was measured by drying the aqueous dispersion of external additive core 1, and an aqueous dispersion of external additive core 1 equivalent to 7.0 parts of solids was taken. To this, 4.0 parts of methyltrimethoxysilane as the shell material and ion-exchanged water were added to make a total volume of 500.0 parts, and the mixture was placed in a mixing vessel equipped with a stirring device. The pH was adjusted to 9.6 with an aqueous sodium bicarbonate solution, and the mixture was stirred at room temperature for 5 hours to obtain a dispersion of external additive 1 in which an organosilicon polymer shell had formed. When the core-shell structure of the external additive was examined using TEM-EDX, an organosilicon polymer shell was formed on the surface of the external additive core, revealing a core-shell structure. The maximum ferret diameter was 150 nm, Tm was 74°C, and Tm-Tc was 10°C.

[0123] <Preparation of external additives 2-11 and 13-15> Dispersions of external additives 2-11 and 13-15 were obtained in the same manner as in the preparation of external additive 1, except that the external additive core, shell material, and number of shell parts were changed as shown in Table 2. When the core-shell structure of the external additive was examined using TEM-EDX, an organosilicon polymer shell was formed on the surface of the external additive core, revealing a core-shell structure. The maximum ferret diameter, Tm, and Tm-Tc are shown in Table 2.

[0124] <Preparation of external additive 12> The solid-liquid ratio of the aqueous dispersion of the external additive Core 3 was measured by allowing it to dry, and an aqueous dispersion of Core 3 equivalent to 7.0 parts of the solid content of Core 3 was collected. Deionized water was added to this aqueous dispersion to make a total volume of 50.0 parts. The pH of this dispersion was measured, and 10% by mass hydrochloric acid was added to adjust the pH to 2.0. Next, 2.5 parts of 3-methacryloxypropyltrimethoxysilane were added as the shell material and placed in a mixing vessel equipped with a stirring device. After heating at 65°C for 30 minutes, 0.25 parts of a 10% by mass aqueous solution of KPS (potassium persulfate) were added and the mixture was heated at 80°C for 3 hours. Subsequently, a dispersion of external additive 12 was obtained by cooling and drying. TEM-EDX analysis of the core-shell structure of the external additive revealed the formation of an organosilicon polymer shell on the surface of the external additive core, thus establishing a core-shell structure. The maximum ferret diameter was 440 nm, and Tm and Tc were not detected.

[0125] <Preparation of Toner Particle Dispersion 1> [Synthesis of polyester resin 1] Polyester resin 1 was synthesized according to the following procedure. The following materials were placed in an autoclave equipped with a vacuum device, water separator, nitrogen gas introduction device, temperature measuring device, and stirring device, and the reaction was carried out for 5 hours at atmospheric pressure and 200°C under a nitrogen atmosphere. • Bisphenol A-propylene oxide 2.0 molar adduct: 77.4 parts Terephthalic acid: 15.8 parts Isophthalic acid: 15.8 parts • Tetrabutoxytitanate: 0.2 parts

[0126] The following ingredients were then added, and the mixture was reacted at 220°C for 3 hours. Trimellitus: 0.1 part • Tetrabutoxytitanate: 0.3 parts The reaction was further carried out under reduced pressure of 10-20 mmHg for 2 hours. The resulting resin was dissolved in chloroform, and this solution was added dropwise to ethanol, reprecipitation occurred, and the mixture was filtered to obtain polyester resin 1. The obtained polyester resin 1 had a Mw of 10200.

[0127] [Synthesis of polyester resin 2] Polyester resin 2 was obtained in the same manner as the synthesis of polyester resin 1, except that trimellitic acid was changed to 1.0 part. The obtained polyester resin 2 had a Mw of 19500.

[0128] [Synthesis of silicon-containing polyester resin] A silicon-containing polyester resin was synthesized using the following procedure. The carboxyl groups in polyester resin 2 and the amino groups in aminosilane were amidated to synthesize a silicon-containing polyester resin as follows. 400.0 parts of N,N-dimethylacetamide were dissolved in 100.0 parts of polyester resin 2, and the following materials were added. The mixture was stirred at room temperature for 5 hours. After the reaction was complete, the solution was added dropwise to methanol, reprecipitation occurred, and the mixture was filtered to obtain a silicon-containing polyester resin. • Silane compound: 3-aminopropyltrimethoxysilane: 1.2 parts • Condensing agent: DMT-MM(4-(4,4-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride): 2.4 parts The silicon concentration of the obtained silicon-containing polyester resin was 0.20% by mass, and its Mw was 19700.

[0129] [Manufacturing of Aqueous Media 1] 390.0 parts of deionized water and 14.0 parts of sodium phosphate (dodecahydrate) [manufactured by Rasa Industries Co., Ltd.] were added to the reaction vessel, and the mixture was kept warm at 65°C for 1.0 hour while purging with nitrogen. Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), a calcium chloride aqueous solution, prepared by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of deionized water, was added all at once while stirring at 12,000 rpm to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 10% hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0, thereby obtaining aqueous medium 1.

[0130] [Production of polymerizable monomer composition 1] • Styrene 60.0 parts • Coloring agent (CI Pigment Blue 15:3) 6.5 parts The above materials were placed in an attritor (manufactured by Nippon Coke Industries Co., Ltd.), and then dispersed using 1.7 mm diameter zirconia particles at 220 rpm for 5.0 hours to prepare dispersion 1 in which the coloring agent was dispersed.

[0131] The following materials were added to dispersion 1. • Styrene 20.0 parts n-butyl acrylate 20.0 parts • Silicon-containing polyester resin 1.0 part • Polyester resin 1 7.0 parts This was kept warm at 65°C, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer to prepare polymerizable monomer composition 1.

[0132] [Granulation process] While maintaining the temperature of the aqueous medium 1 at 70°C and the rotation speed of the stirring device at 12,000 rpm, polymerizable monomer composition 1 was added to the aqueous medium 1, and 9.0 parts of t-butyl peroxypivalate, a polymerization initiator, were added. Granulation was then carried out for 10 minutes while maintaining the stirring speed at 12,000 rpm.

[0133] [Polymerization process] The high-speed stirring device was replaced with a stirrer equipped with propeller blades, and polymerization was carried out for 5.0 hours while stirring at 150 rpm and maintaining a temperature of 70°C. The polymerization reaction was then carried out by raising the temperature to 85°C and heating for another 2.0 hours to obtain toner particle dispersion liquid 1.

[0134] <Preparation of Toner Particle Dispersion 2> Toner particle dispersion 2 was manufactured in the same manner as in the manufacture of toner particle dispersion 1, except that the amount of silicon-containing polyester resin was changed to 0 parts.

[0135] <Preparation of Toner Particle Dispersion 3> [Manufacturing of Resin Particle Dispersion 1] The following materials were weighed, mixed, and dissolved. • Styrene 82.6 parts • n-butyl acrylate 9.2 parts • Acrylic acid 1.3 parts • Hexanediol diacrylate 0.4 parts n-lauryl mercaptan 3.2 parts A 10% aqueous solution of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to the obtained solution and dispersed. While slowly stirring for 10 minutes, an aqueous solution of 0.15 parts potassium persulfate dissolved in 10.0 parts deionized water was added. After nitrogen purging, emulsion polymerization was carried out at 70°C for 6.0 hours. After polymerization was complete, the reaction solution was cooled to room temperature, and deionized water was added to obtain resin particle dispersion 1 with a solid content of 12.5% ​​and a volume-based median diameter of 0.2 μm.

[0136] [Manufacturing of colorant particle dispersion] The following materials were weighed and mixed. • Coloring agent (CI Pigment Blue 15:3) 100.0 parts • Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 15.0 units • Ion-exchanged water 885.0 parts The above materials were dispersed for 1 hour using a wet jet mill JN100 (manufactured by Jokoh Co., Ltd.) to obtain a dispersion of colorant particles.

[0137] [Formation of aggregated particles] ·Resin particle dispersion 1 160.0 parts • 10.0 parts of colorant particle dispersion • Magnesium sulfate 0.2 parts The above materials were dispersed using a homogenizer (IKA Ultra-Turrax T50), and then heated to 65°C while stirring. After stirring at 65°C for 1.0 hour, 20.0 parts of resin particle dispersion 1 were added and the mixture was stirred for a further 0.2 hours. Observation with an optical microscope confirmed the formation of aggregated particles with a number-average particle size of 7.0 μm. After adding 2.2 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), the mixture was heated to 80°C and stirred for 2.0 hours to obtain a dispersion of fused spherical toner particles 3.

[0138] <Preparation of toner particles 4> The following materials were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet pipe. Terephthalic acid 29.0 parts • Polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane 80.0 copies • Titanium dihydroxybis(triethanolamine) 0.1 part The mixture is then heated to 200°C and reacted for 9 hours while introducing nitrogen and removing the water produced. Furthermore, 5.8 parts of trimellitic anhydride were added, and the mixture was heated to 170°C and reacted for 3 hours to synthesize polyester resin 3 as a binder resin.

[0139] • Low-density polyethylene (melting point: 100°C) 20.0 parts • Styrene 64.0 parts • n-butyl acrylate 13.5 parts 2.5 parts acrylonitrile Furthermore, the above materials were placed in an autoclave, the system was purged with nitrogen, and then maintained at 180°C while heating and stirring. 50.0 parts of a xylene solution of 2.0% t-butyl hydroperoxide were continuously added dropwise to the system over 4.5 hours. After cooling, the solvent was separated and removed to obtain a graft polymer in which a copolymer (styrene, n-butyl acrylate, and acrylonitrile copolymer) was grafted onto polyethylene.

[0140] • Polyester resin 3 100.0 parts • Graft polymer 5.0 parts CI Pigment Blue 15:3 5.0 parts The above materials were thoroughly mixed in an FM mixer (FM-75 model, manufactured by Nippon Coke Industries Co., Ltd.), and then melt-kneaded in a twin-shaft kneader (PCM-30 model, manufactured by Ikegai Iron Works Co., Ltd.) set to a temperature of 100°C. The resulting mixture was cooled and then coarsely ground to a size of 1 mm or less using a hammer mill to obtain a coarse material. Next, the obtained crushed material was finely pulverized to obtain a finely pulverized material of about 5 μm using a turbo mill (T-250: RSS rotor / SNB liner) manufactured by Turbo Industry Co., Ltd. Thereafter, fine powder and coarse powder were cut using a multi-stage classifier utilizing the Coanda effect to obtain toner particles 4.

[0141] <Preparation of toner particle dispersion liquid 5> The solid-liquid ratio was measured by drying the toner particle dispersion liquid 1, and the toner particle dispersion liquid 1 corresponding to 100 parts of the solid content was separated. This was heated to 55°C and mixed using a propeller stirring blade, and the pH of the mixed liquid was adjusted to 5.6 using hydrochloric acid or a sodium hydrogen carbonate solution. 2.8 parts of methyltrimethoxysilane was added thereto and stirred, and the pH was adjusted to 9.6 using an aqueous sodium hydrogen carbonate solution. The mixture stirred and held at 55°C for 4 hours was air-cooled to obtain toner particle dispersion liquid 5.

[0142] <Preparation of toner particle dispersion liquid 6> In the production of the toner particle dispersion liquid 1, a toner particle dispersion liquid 6 was produced in the same manner except that the silicon-containing polyester resin (1.0 part) was changed to HNP-9 (7.0 parts).

[0143] <Production of toner 1> The solid-liquid ratio was measured by drying the toner particle dispersion liquid 1, and the toner particle dispersion liquid 1 corresponding to 100.0 parts of the solid content was separated. Next, the solid-liquid ratio was measured by drying the dispersion liquid of external additive 1, and the dispersion liquid of external additive 1 corresponding to 5.0 parts of the solid content was added to the toner particle dispersion liquid 1 and heated to 55°C. The pH of the mixed liquid was adjusted to 5.6 using hydrochloric acid or a sodium hydrogen carbonate solution while mixing using a propeller stirring blade, stirred and held at 100°C for 1 hour, and then air-cooled. Thereafter, the pH was adjusted to 1.5 with 1 mol / L hydrochloric acid, stirred for 1 hour, and filtered while washing with ion-exchanged water to obtain toner 1. When the toner 1 obtained this time was evaluated by TOF-SIMS, it was confirmed that the surface of the toner particles contained carbon atoms and silicon atoms.

[0144] <Production of toner 2> In the manufacture of toner 1, the toner particle dispersion 1 is dispersed with the toner particle dispersion 5 and the external additive 1. Toner 2 was obtained in the same manner, except that the liquid was changed to a dispersion of external additive 2. When the obtained toner 2 was evaluated by TOF-SIMS, it was confirmed that carbon atoms and silicon atoms were contained on the surface of the toner particles.

[0145] <Manufacturing of toners 3-6, 10, 11, and comparative toners 1-4> In the production of Toner 1, Toners 3-6, 10, 11, and Comparative Toners 1-4 were obtained in the same manner, except that the types of toner particle dispersion and external additive dispersion were changed according to Table 3.

[0146] <Manufacturing of Toner 7> The solid-liquid ratio was measured by drying the toner particle dispersion 3, and a portion of the toner particle dispersion 3 equivalent to 100.0 parts of solids was collected. Next, the solid-liquid ratio was measured by drying the dispersion of the external additive 7, and a dispersion of the external additive 7 equivalent to 5.0 parts of solids was added, and the mixture was heated to 55°C. The pH of the mixture was adjusted to 5.6 using hydrochloric acid or sodium bicarbonate solution while mixing with a propeller agitator, and after stirring at 100°C for 1 hour, it was air-cooled. The mixture was then filtered, and the filtered solid was washed with 720.0 parts of deionized water for 1 hour with stirring. The solution containing the toner was filtered and dried using a vacuum dryer to obtain toner 7.

[0147] <Manufacturing of Toner 8> The dispersion of external additive 8 was washed with deionized water, filtered, and vacuum-dried to obtain the powder of external additive 8. Next, 1.0 part of the powder of external additive 8 was taken from 100 parts of the powder of toner particles 4 and mixed for 5 minutes in a Henschel mixer (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) to obtain toner 8. The jacket temperature of the Henschel mixer was set to 10°C and the peripheral speed of the rotating blades was set to 38 m / sec.

[0148] <Manufacturing of Toner 9> The dispersion of external additive 9 was washed with deionized water, filtered, and vacuum-dried to obtain the powder of external additive 9. Next, the toner particle dispersion 2 was adjusted to a pH of 1.5 with 1 mol / L hydrochloric acid, stirred for 1 hour, and then filtered while washing with deionized water to obtain toner particles 2. For every 100 parts of toner particles 2, 1.0 part of external additive 9 powder was taken and mixed for 5 minutes in a Henschel mixer (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) to obtain toner 9. The jacket temperature of the Henschel mixer was set to 10°C, and the peripheral speed of the rotating blades was set to 38 m / sec.

[0149] <Evaluation of image streaks after endurance> The image streaks are vertical streaks of about 0.5 mm in length that occur when the core-shell type external additive deforms, exposing the internal release agent and contaminating the material. This is an image defect that is easily observed when outputting a full-surface halftone image. A modified Canon LBP712Ci was used as the image forming machine. The process speed of the main unit was modified to 250 mm / sec. Necessary adjustments were made to enable image forming under these conditions. In addition, the toner was removed from the black and cyan cartridges and replaced with 50g each of evaluation toner. The toner load was 1.0 mg / cm². 2 That's what I decided.

[0150] Image streaking during continuous use under normal temperature and humidity conditions (23°C, 60%RH) was evaluated. Xerox 4200 paper (Xerox Corporation, 75g / m²) was used as the evaluation paper. 2 ) was used. Under normal temperature and humidity conditions, 15,000 intermittent continuous prints were performed, outputting two "E" character images with a 1% print density every four seconds. Afterwards, a 50% halftone image was printed across the entire surface, and the presence or absence of streaks was observed. The evaluation results at this time were defined as "endurance streaks" (image streaks after durability). Grades A through C were judged as good. The evaluation results are shown in Table 4. (Evaluation Criteria) A: No streaks or toner clumps have appeared. B: There are no spotted streaks, but there are one or two small toner clumps. C: There are 1-2 spotted streaks at the edges, or 3-4 small toner clumps. D: There are 1-2 spotty streaks or 5-6 small toner clumps all over the surface. E: There are three or more spotted streaks across the entire surface, or seven or more small toner clumps.

[0151] <Evaluation of secure wrapping> The same image forming apparatus used for evaluating image streaks was modified to allow for adjustment of the fixing temperature. GF-600 (Canon Marketing Japan Inc., 60g / m²) was used as the evaluation paper. 2 The following was used: The output image was set to a solid color and evaluated under normal temperature and humidity conditions (23°C, 60%RH). The toner under evaluation was fixed while changing the fixing temperature from 140°C in 5°C increments, and the paper feeding condition was visually checked. The fixing wrap-around was evaluated based on the fuser temperature when paper was fed through without wrap-around, according to the following criteria. The evaluation results are shown in Table 4. A: Below 150℃ B: 150℃ or higher but less than 155℃ C: 155℃ or higher, less than 160℃ D: 160℃ or higher, but less than 170℃ E: Above 170℃

[0152] <Evaluation of the brake performance after endurance testing> Using the same image forming apparatus as used for evaluating image streaks, the fogging after continuous use under normal temperature and humidity conditions (23°C, 60% RH) was evaluated. Xerox 4200 paper (Xerox Corporation, 75 g / m²) was used as the paper for durability testing. 2 ) was used. Under normal temperature and humidity conditions, 15,000 intermittent continuous prints were performed, outputting two "E" character images with a print density of 1% every four seconds.

[0153] Next, in gloss paper mode (1 / 3 speed), HP Brochure Paper 200g, Glossy (basis weight 200g / cm²) in Letter size was used as the evaluation paper. 2Using [the relevant item], a solid white image with a printing ratio of 0% was printed out. Using a "REFLECTMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.), the whiteness of the white background portion of the solid white image and the whiteness of the transfer paper were measured. The difference between these whitenesses was taken as the fog density (%) to evaluate image fog (permanent fog). An amber filter was used as the filter. A smaller numerical value indicates a better evaluation. The evaluation criteria are as follows. A to C were judged to be good. The evaluation results are shown in Table 4. (Evaluation Criteria) A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more and less than 3.0% D: 3.0% or more and less than 4.0% E: 4.0% or more

[0154] (Evaluation of Charge Rise Characteristics under High Temperature and High Humidity Environment) Under a high temperature and high humidity environment (30 °C, 80% RH), the following evaluation was carried out. Prepare two samples by putting 19.0 g of magnetic carrier F813-300 (manufactured by Powdertech Co., Ltd.) and 1.0 g of the evaluation toner into a 50 mL plastic bottle with a lid. Using a shaker (YS-LD: manufactured by Yayoiken Co., Ltd.), shake at a speed of 4 reciprocations per second for 2 minutes or 10 minutes respectively to prepare a two-component developer. Put 0.200 g of the two-component developer to be measured for the triboelectric charge into the metal measuring container 2 with a 500-mesh (opening size 25 μm) screen 3 at the bottom shown in Figure 1, and cover it with a metal lid 4. At this time, weigh the total mass of the measuring container 2 as W1 (g). Next, in the suction machine 1 (the part in contact with the measuring container 2 is at least an insulator), suck from the suction port 7, and adjust the air volume control valve 6 to make the pressure of the vacuum gauge 5 50 mmAq. In this state, suck the toner for 1 minute and remove it. Let the potential of the potentiometer 9 at this time be V (volt). Here, 8 is a capacitor with a capacitance of C (μF). Weigh the total mass of the measuring container after suction as W2 (g). The triboelectric charge of this toner is calculated by the following formula. Triboelectric charge (mC / kg) = (C × V) / (W1 - W2) The formula "amount of triboelectric charge after 2 minutes of shaking" / "amount of triboelectric charge after 10 minutes of shaking" × 100 was calculated, and the result was defined as the charge rise rate. The evaluation was then performed according to the following criteria. The evaluation results are shown in Table 4. A: Static electricity build-up rate is 90% or higher B: Charging rise rate is 80% or more but less than 90% C: Electrostatic rise rate is 70% or more but less than 80% D: Charging rise rate is 60% or more but less than 70% E: Electrostatic rise rate is less than 60%

[0155] [Table 1]

[0156] [Table 2]

[0157] [Table 3] In the table, the Ferret diameter is the maximum Ferret diameter of a core-shell type particle. The presence or absence of silicon and carbon is indicated by TOF-SIMS analysis: "Present" if carbon and silicon atoms are detected on the toner particle surface, and "Absent" if they are not detected.

[0158] [Table 4] [Explanation of Symbols]

[0159] 1: Suction device, 2: Measuring container, 3: Screen, 4: Lid, 5: Vacuum gauge, 6: Air volume control valve, 7: Suction port, 8: Condenser, 9: Potential meter

[0160] This disclosure relates to the following configuration. (Composition 1) A core-shell type particle having a core and a shell on the surface of the core, The core contains a crystalline release agent, The sum of the number mean and standard deviation of the Ferret diameter of the particles is between 20 and 500 nm. The shell contains an organosilicon polymer, In differential scanning calorimetry of the particles, When the temperature is increased from 30°C to 120°C at a rate of 10.0°C / min, a maximum endothermic peak is observed. The maximum heat generation peak occurred when the temperature was reduced from 120°C to 30°C at a rate of 10.0°C / min. When the peak temperature of the maximum endothermic peak is denoted as Tm (°C) and the peak temperature of the maximum exothermic peak is denoted as Tc (°C), if Tc is 5°C or more lower than Tm, A core-shell type particle characterized by the following features. (Configuration 2) A core-shell type particle having a core and a shell on the surface of the core, The core contains hydrocarbon wax, The sum of the number mean and standard deviation of the Ferret diameter of the particles is between 20 and 500 nm. The shell contains an organosilicon polymer, In differential scanning calorimetry of the particles, When the temperature is increased from 30°C to 120°C at a rate of 10.0°C / min, a maximum endothermic peak is observed. The maximum heat generation peak occurred when the temperature was reduced from 120°C to 30°C at a rate of 10.0°C / min. When the peak temperature of the maximum endothermic peak is denoted as Tm (°C) and the peak temperature of the maximum exothermic peak is denoted as Tc (°C), if Tc is 5°C or more lower than Tm, A core-shell type particle characterized by the following features. (Composition 3) The organosilicon polymer comprises a core-shell type particle according to configuration 1 or 2, which includes a structure represented by the following formula (RT3). R-SiO 3 / 2 ...(RT3) [In formula (RT3), R represents an alkyl group having 1 to 6 carbon atoms.] (Composition 4) The solid of the aforementioned organosilicon polymer 29 In Si-NMR measurements, when RT3 is the area of ​​the peak corresponding to the structure represented by the above formula (RT3), and S is the sum of the areas of the peaks in M ​​units, D units, T units, and Q units, A core-shell type particle as described in configuration 3, wherein the ratio of RT3 to S (RT3 / S) is between 0.50 and 1.00. (Composition 5) A core-shell type particle having a core and a shell on the surface of the core, The core contains hydrocarbon wax, The sum of the number mean and standard deviation of the Ferret diameter of the particles is between 20 and 500 nm. The shell contains an organosilicon polymer, The organosilicon polymer contains a structure represented by the following formula (RT3): A core-shell type particle characterized by the following features. R-SiO 3 / 2 ...(RT3) [In formula (RT3), R represents an alkyl group having 1 to 6 carbon atoms.] (Composition 6) The solid of the aforementioned organosilicon polymer 29 In Si-NMR measurements, when RT3 is the area of ​​the peak corresponding to the structure represented by the above formula (RT3), and S is the sum of the areas of the peaks in M ​​units, D units, T units, and Q units, A core-shell type particle as described in configuration 5, wherein the ratio of RT3 to S (RT3 / S) is between 0.50 and 1.00. (Composition 7) A core-shell type particle according to any of configurations 1 to 6, wherein the Tm is 100°C or less. (Configuration 8) The kinematic viscosity of the core at 110°C is 1 to 60 mm 2 / second, configuration 1-7 A core-shell type particle as described below. (Composition 9) The core-shell particle according to any one of configurations 1 to 8, wherein the organosilicon polymer is a condensed polymer of at least one organosilicon compound selected from the group consisting of organosilicon compounds having a structure represented by the following formula (Z). TIFF2023176415000006.tif36153 In formula (Z), R a R is an alkyl group having 1 to 6 carbon atoms. 1 , R 2 and R 3 Each of these is an independent alkoxy group having 1 to 6 carbon atoms. (Composition 10) Core-shell type particles described in any of components 1 to 9, which are external additives for toner. (Composition 11) A toner comprising toner particles having a binder resin, and an external additive on the surface of the toner particles, A toner characterized in that the external additive is a core-shell type particle as described in any of the components 1 to 10. (Composition 12) The toner according to configuration 11, wherein carbon atoms and silicon atoms are detected when time-of-flight secondary ion mass spectrometry is performed on the surface of the toner particles.

Claims

1. A core-shell type particle having a core and a shell on the surface of the core, wherein the core contains a crystalline release agent, the sum of the number average value and the standard deviation of the Feret diameter of the particles is 20 to 500 nm, the shell contains an organosilicon polymer, in the differential scanning calorimetry of the particles, when the temperature is raised from 30 °C to 120 °C at 10.0 °C / min, a maximum endothermic peak exists, when the temperature is lowered from 120 °C to 30 °C at 10.0 °C / min, a maximum exothermic peak exists, when the peak temperature of the maximum endothermic peak is Tm (°C) and the peak temperature of the maximum exothermic peak is Tc (°C), the Tc is 5 °C or more lower than the Tm, A core-shell type particle characterized by the above.

2. A core-shell type particle having a core and a shell on the surface of the core, wherein the core contains a hydrocarbon wax, the sum of the number average value and the standard deviation of the Feret diameter of the particles is 20 to 500 nm, the shell contains an organosilicon polymer, in the differential scanning calorimetry of the particles, when the temperature is raised from 30 °C to 120 °C at 10.0 °C / min, a maximum endothermic peak exists, when the temperature is lowered from 120 °C to 30 °C at 10.0 °C / min, a maximum exothermic peak exists, when the peak temperature of the maximum endothermic peak is Tm (°C) and the peak temperature of the maximum exothermic peak is Tc (°C), the Tc is 5 °C or more lower than the Tm, A core-shell type particle characterized by the above.

3. The core-shell type particle according to claim 1 or 2, wherein the organosilicon polymer contains a structure represented by the following formula (RT3). R—SiO ３／２ ・・・(RT3) [In formula (RT3), R represents an alkyl group having 1 to 6 carbon atoms.]

4. The solid of the organosilicon polymer ２９ In the Si-NMR measurement, when the area of the peak corresponding to the structure represented by the formula (RT3) is defined as RT3, and the sum of the areas of the peaks of the M unit, D unit, T unit, and Q unit is defined as S The core-shell type particle according to claim 3, wherein the value of the ratio of RT3 to S (RT3 / S) is 0.50 to 1.

00. The M unit is (Ri)(Rj)(Rk)SiO1 / 2, The D unit is (Rg)(Rh)Si(O1 / 2)2, The T unit is RmSi(O1 / 2)3, The Q unit is Si(O1 / 2)4, Ri, Rj, Rk, Rg, Rh, Rm represent alkyl groups bonded to silicon.

5. A core-shell type particle having a core and a shell on the surface of the core, wherein the core contains a hydrocarbon wax, the sum of the number average value and the standard deviation of the Feret diameter of the particles is 20 to 500 nm, The shell contains an organosilicon polymer, The organosilicon polymer contains a structure represented by the following formula (RT3), A core-shell type particle characterized by the above. R—SiO ３／２ ・・・(RT3) [In formula (RT3), R represents an alkyl group having 1 to 6 carbon atoms. ]

6. The solid of the organosilicon polymer ２９ In the Si-NMR measurement, when the area of the peak corresponding to the structure represented by the formula (RT3) is defined as RT3, and the sum of the areas of the peaks of the M unit, D unit, T unit, and Q unit is defined as S The core-shell type particle according to claim 5, wherein the value of the ratio of RT3 to S (RT3 / S) is 0.50 to 1.

00. [The M unit is (Ri)(Rj)(Rk)SiO1 / 2, The D unit is (Rg)(Rh)Si(O1 / 2)2, The T unit is RmSi(O1 / 2)3, The Q unit is Si(O1 / 2)4, Ri, Rj, Rk, Rg, Rh, Rm represent alkyl groups bonded to silicon. ]

7. The core-shell type particle according to claim 1 or 2, wherein the Tm is 100°C or lower.

8. The kinematic viscosity of the core at 110 °C is 1 to 60 mm ２ / s, and the core-shell type particle according to claim 1, 2 or 5.

9. The core-shell type particle according to claim 1, 2 or 5, wherein the organosilicon polymer is a polycondensate of at least one organosilicon compound selected from the group consisting of organosilicon compounds having a structure represented by the following formula (Z). In formula (Z), R ａ is an alkyl group having 1 to 6 carbon atoms. R １ , R ２ and R ３ are each independently an alkoxy group having 1 to 6 carbon atoms.

10. The core-shell type particle according to claim 1, 2 or 5, which is an external additive for toner.

11. A toner having toner particles having a binder resin and an external additive on the surface of the toner particles, The toner is characterized in that the external additive is the core-shell type particle according to claim 1, 2 or 5.

12. The toner according to claim 11, wherein carbon atoms and silicon atoms are detected when time-of-flight secondary ion mass spectrometry is performed on the surface of the toner particles.

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