toner

Abstract

To provide a toner which prevents an adverse effect on images caused by toner agglomeration, even when image output is performed for a long period of time under high temperature and high humidity environment after having been stored in a severe environment.SOLUTION: A toner contains toner particles containing a binder resin and a hydrocarbon wax, and inorganic fine particles, wherein the inorganic fine particles contain silica fine particles surface-treated with specific polydimethylsiloxane, a total amount of trimethylsilanol of the silica fine particles is 1.0 ppm or more and 5.0 ppm or less, when a standard value of an ion amount of an ester group is measured by time-of-flight secondary ion mass spectrometry, one or more peaks of the standard value exist within a range of 100 nm from the surface of the toner particles, and a maximum value A (dmax) in the peak of the standard value and the standard value A (0) on the surface of the toner particles satisfy the following relations: 1.05≤A(dmax) / A(0)≤5.00, and A(0)≥0.010.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to toner used in an electrophotographic image forming apparatus. [Background technology]

[0002] Image forming devices that utilize electrophotographic technology, such as photocopiers and printers, are facing increasing demands for miniaturization, higher speed, higher image quality, and greater stability. To achieve compact devices, for example, fixing components such as rollers and films used to fix toner to recording media such as paper are being simplified. However, when fixing components such as rollers and films are simplified, the toner is not sufficiently heated and pressurized at the fixing nip, so the release agent inside the toner cannot seep out sufficiently, and the toner adheres to the fixing film (hereinafter referred to as low-temperature offset). To address this problem, toners containing hydrocarbon wax as a release agent in the toner particles have been proposed for some time.

[0003] In addition to these requirements, toners are also subject to harsh conditions during transportation from manufacturing to consumer use, and therefore require durability to withstand such transportation. However, when toners containing hydrocarbon wax within the toner particles are stored in harsh environments with rapid changes in temperature and humidity, the hydrocarbon wax inside the toner particles can seep out to the surface of the toner particles. This hydrocarbon wax seeping out to the surface of the toner particles can increase the adhesion of the toner and cause toner aggregates to form.

[0004] In the case of a single-component developer, the toner aggregates that form remain in the friction area between the toner carrier and the charge-applying element, causing image defects (vertical streaks in halftone images). In particular, if the toner is stored in a harsh environment with rapid changes in temperature and humidity, and then used for a long period in a high-temperature, high-humidity environment, the toner aggregates formed by the leaching of hydrocarbon wax grow, making the above image defects more pronounced. In other words, conventional toners containing hydrocarbon wax need to be improved in terms of storage and durability so that they are less affected when stored in a harsh environment and then used for long periods of time in a high-temperature, high-humidity environment.

[0005] Therefore, as a method to further improve the shelf life and durability of toners containing hydrocarbon waxes, toners with silica microparticles coated with highly hydrophobic silicone oil and toners with a heat-resistant shell on the surface of the toner particles are being considered. Patent Document 1 proposes a toner to which silica nanoparticles hydrophobized with polydimethylsiloxane having a specific viscosity and modified side chains are added. Patent Document 2 proposes a toner in which toner particles are coated with a heat-resistant, highly polar amorphous polyester resin, and silica nanoparticles hydrophobized with polydimethylsiloxane are added. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2009-157161 [Patent Document 2] Japanese Patent Publication No. 2017-044981 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] As a result of the inventors' investigation, the toner described in Patent Document 1 is made possible by adding silica fine particles hydrophobized with highly hydrophobic polydimethylsiloxane to the toner particles, which is effective in high temperature and high humidity environments. It is believed that the toner's fluidity and durability have been improved. However, when the toner was stored in a harsh environment with rapid changes in temperature and humidity, it was found that toner aggregates, presumably caused by the leaching of hydrocarbon wax, formed, resulting in image defects. In other words, there is room for improvement in its storage capabilities in harsh environments with rapid changes in temperature and humidity.

[0008] The toner described in Patent Document 2 has toner particles coated with a heat-resistant, highly polar, amorphous polyester resin. Furthermore, it is believed that by adding silica fine particles treated with highly hydrophobic polydimethylsiloxane to the toner, the leaching of hydrocarbon wax from inside the toner particles is suppressed, while improving fluidity and electrostatic properties in high-temperature, high-humidity environments. However, similar to Patent Document 1, it was found that when the toner is stored in a harsh environment where temperature and humidity change rapidly, toner aggregates, presumably caused by the leaching of hydrocarbon wax, occur, resulting in image defects.

[0009] This disclosure provides a toner that is less prone to image defects caused by toner agglomeration, even when stored in a harsh environment and then subjected to long-term image output in a high-temperature, high-humidity environment. [Means for solving the problem]

[0010] A toner containing toner particles containing a binder resin and hydrocarbon wax, and inorganic fine particles, The inorganic fine particles contain silica fine particles surface-treated with polydimethylsiloxane represented by the following formula (A) and polydimethylsiloxane represented by the following formula (B). In the analysis of organic volatile components of the silica fine particles by headspace method at a heating temperature of 150°C, the total amount of trimethylsilanol in terms of octamethyltrisiloxane, based on the mass of the silica fine particles, was 1.0 ppm or more and 5.0 ppm or less. By time-of-flight secondary ion mass spectrometry, measuring from the surface of the toner particles to a depth of 100 nm, when the value obtained by dividing the ion amount of the structure represented by the following formula (C) by the total ion amount counted is defined as the standard value, within a range of 100 nm or less from the surface of the toner particles, there is one or more peaks of the standard value, when the maximum value among the peaks of the standard value is A(dmax) and the standard value at the surface of the toner particles is A(0), a toner characterized in that the A(dmax) and the A(0) satisfy the following formulas (1) and (2). 1.05 ≦ A(dmax) / A(0) ≦ 5.00 ···(1) A(0) ≧ 0.010 ···(2) (In formula (B), R , , [Figure 2] , [Figure 1] , , , ,

[0012] , , , , , , ,

[0013] , , is a carbinol group, a hydroxy group, an epoxy group, a carboxy group, an alkyl group, or a hydrogen atom, and R 2 is a carbinol group, a hydroxy group, an epoxy group, a carboxy group, or a hydrogen atom. n and m are average repeating unit numbers, and respectively, n is 30 or more and 200 or less, and m is 30 or more and 200 or less. The methyl groups in the side chains in formula (B) may each be substituted with a carbinol group, a hydroxy group, an epoxy group, a carboxy group, or a hydrogen atom.)

[0011]

Chemical formula

Advantages of the Invention

[0012] According to the present disclosure, it is possible to provide a toner in which image defects caused by toner agglomerates are unlikely to occur even when image output is performed for a long time in a high-temperature and high-humidity environment after storage in a harsh environment.

Brief Description of the Drawings

[0013] [Figure 1] Time chart of heat cycle [Figure 2] Schematic diagram of analysis result of time-of-flight secondary ion mass spectrometry of toner [Modes for carrying out the invention]

[0014] When a numerical range is expressed as "XX or greater and YY or less" or "XX to YY," unless otherwise specified, it means a numerical range that includes the lower and upper limits. When a numerical range is expressed in steps, the upper and lower limits of each range can be combined in any way.

[0015] The inventors of this invention have diligently studied a toner containing hydrocarbon wax that can provide high-quality images even when stored in a harsh environment and then subjected to long-term image output in a high-temperature, high-humidity environment.

[0016] To date, approaches to improving the shelf life and durability of toners containing hydrocarbon waxes have included forming a highly polar, heat-resistant shell on the surface of the toner particles and adding hydrophobically treated silica microparticles to the surface of the toner particles. By providing a highly polar, heat-resistant shell on the surface of the toner particles, the leaching of hydrocarbon wax from inside the toner particles can be suppressed due to the difference in polarity, thereby improving shelf life. Furthermore, by adding hydrophobically treated silica microparticles to the surface of the toner, the decrease in toner fluidity when used for a long period of time in a high-temperature, high-humidity environment can be suppressed, thus improving durability. It can be improved.

[0017] However, considering the shelf life in harsh environments with rapid changes in temperature and humidity, and the durability after storage in such harsh environments, the hydrocarbon wax contained within the toner particles has higher thermal mobility than binder resins, and is more likely to seep out onto the surface of the toner particles when the temperature rises or falls. In particular, the hydrocarbon wax readily adheres to the polydimethylsiloxane on the surface of the silica microparticles, making it easier for the hydrocarbon wax to seep out onto the surface of the toner particles. This increases the adhesion of the toner and makes it easier for toner aggregates to form. For example, in the case of a single-component developer, the formed toner aggregates remain in the contact area between the toner carrier and the charge-applying member. As a result, the toner is not sufficiently charged, leading to a decrease in density, fogging where toner is developed in non-image areas, or vertical streaks in halftone images.

[0018] Patent Document 1 proposes a toner to which silica nanoparticles, which have been hydrophobized with polydimethylsiloxane whose side chains have been modified with hydroxyl or phenyl groups, are added. The silica nanoparticles described in Patent Document 1 have functional groups on the side chains of the polydimethylsiloxane, so they are highly reactive with silica, and the amount of polydimethylsiloxane that migrates to the surface of the toner particles is reduced. As a result, the adhesion of the toner is increased and the decrease in toner fluidity is suppressed.

[0019] However, this toner has a vinyl resin on its surface, which has lower polarity compared to polyester resins, etc., making it more compatible with the polydimethylsiloxane on the surface of the silica microparticles, thus reducing the shell's ability to shield against hydrocarbon wax. As a result, it is thought that the leakage of hydrocarbon wax cannot be suppressed when stored in a harsh environment, and toner aggregates are formed. Therefore, when used for a long period in a high-temperature, high-humidity environment after being stored in a harsh environment, image defects caused by toner aggregates occur.

[0020] On the other hand, Patent Document 2 proposes a toner having a shell of heat-resistant, highly polar amorphous polyester resin on the surface of the toner particles, and silica fine particles hydrophobized with polydimethylsiloxane as shown in formula (A). However, it has been found that even with such a toner, image defects caused by toner aggregates occur.

[0021] The inventors believe the reason for the above-mentioned image defects is as follows: First, when silica nanoparticles hydrophobized with polydimethylsiloxane represented by formula (A) are surface-treated, a portion of the polydimethylsiloxane reacts with the silica core and adheres to the silica nanoparticles. The inventors believe that when polydimethylsiloxane represented by formula (A) reacts with the silica core, the trimethylsilyl group at the end of the polydimethylsiloxane is removed, changing the end to a silanol group, which then reacts with the silica core. For this reason, silica nanoparticles hydrophobized with polydimethylsiloxane represented by formula (A) contain trimethylsilanol, which is a by-product.

[0022] Next, trimethylsilanol is a basic substance and is polar. Therefore, trimethylsilanol tends to be compatible with the highly polar toner particle surface due to electrostatic interactions. In addition, polydimethylsiloxane and trimethylsilanol contained in silica microparticles both contain trimethylsilyl groups and therefore tend to be compatible. As a result, as the amount of trimethylsilanol in the silica microparticles increases, trimethylsilanol acts as a bridge between the polydimethylsiloxane in the silica microparticles and the highly polar toner particle surface. Consequently, a portion of the polydimethylsiloxane represented by formula (A) in the silica microparticles becomes compatible with the highly polar shell. When the shell on the toner surface becomes compatible with a portion of the hydrophobic polydimethylsiloxane, the shielding ability of the shell against hydrocarbon wax decreases.

[0023] When the shell's shielding ability against hydrocarbon waxes is reduced, and temperature and humidity change rapidly... When stored in harsh environments, hydrocarbon wax contained within toner particles becomes more likely to seep out. As a result, the hydrocarbon wax seeps out onto the toner surface, increasing the toner's adhesion and making it more prone to toner agglomeration. In addition, the inventors believe that when used for extended periods in high-temperature and high-humidity environments, vertical streaks may appear in halftone images due to toner agglomeration that occurred during storage in harsh environments.

[0024] As a result of diligent research by the inventors, we have found that, with the following configuration, a toner containing hydrocarbon wax can provide high-quality images even when stored in a harsh environment and then subjected to long-term image output in a high-temperature, high-humidity environment.

[0025] In other words, this disclosure relates to a toner containing toner particles containing a binder resin and a hydrocarbon wax, and inorganic fine particles, The inorganic fine particles contain silica fine particles surface-treated with polydimethylsiloxane represented by the following formula (A) and polydimethylsiloxane represented by the following formula (B). In the analysis of organic volatile components of the silica fine particles by headspace method at a heating temperature of 150°C, the total amount of trimethylsilanol in terms of octamethyltrisiloxane, based on the mass of the silica fine particles, was 1.0 ppm or more and 5.0 ppm or less. When the amount of ions in the toner particle is measured from the surface down to a depth of 100 nm using time-of-flight secondary ion mass spectrometry, and the amount of ions in the structure shown in the following formula (C) is divided by the total amount of ions counted, the standard value is defined as follows: Within a range of 100 nm from the surface of the toner particles, there is one or more peaks of the specified value. [ka] When the maximum value among the peaks of the specified value is defined as A(dmax), and the specified value on the surface of the toner particles is defined as A(0), A toner characterized by satisfying the following formulas (1) and (2). 1.05≦A(dmax) / A(0)≦5.00 (1) A(0)≧0.010 ···(2) [ka] (In the formula, R 1 R is a carbinol group, hydroxyl group, epoxy group, carboxyl group, alkyl group, or hydrogen atom. 2 is a carbinol group, hydroxyl group, epoxy group, carboxyl group, or hydrogen atom. n and m are the average number of repeating units, where n is between 30 and 200, and m is between 30 and 200. The methyl group (-CH3) in the side chain of formula (B) may be substituted with a carbinol group, hydroxyl group, epoxy group, carboxyl group, or hydrogen atom, respectively.

[0026] Here, we will explain why the above-mentioned performance can be imparted by treating silica nanoparticles with polydimethylsiloxanes represented by formulas (A) and (B) and controlling the amount of trimethylsilanol in the silica nanoparticles and the distribution of ester group concentration near the toner surface. The inventors have found that the following points are important in order to suppress the leaching of hydrocarbon wax when a toner containing hydrocarbon wax is stored in a harsh environment, and to suppress image defects when used for a long period of time in a high-temperature, high-humidity environment after being stored in a harsh environment.

[0027] (1-1) The amount of trimethylsilanol in the silica microparticles containing polydimethylsiloxane is low, and the polydimethylsiloxane contained in the silica microparticles does not easily adhere to the surface of the toner particles. (1-2) In the region near the toner particle surface, within a depth of 100 nm from the toner particle surface, there are areas where the ester group concentration is higher than on the toner particle surface and at a depth of 100 nm from the toner particle surface. That is, the standard value of the ester group ion fragment described later has one or more peaks, suppressing the seepage of hydrocarbon wax from inside the toner.

[0028] The above (1-1) is strongly influenced by the composition of polydimethylsiloxane, which is the surface treatment agent for silica microparticles, and the resin composition on the surface of the toner particles. The low trimethylsilanol content in the silica microparticles and the poor adhesion between the polydimethylsiloxane of the silica microparticles and the surface of the toner particles suppress the amount of hydrocarbon wax seeping out from inside the toner particles when stored in harsh environments. Therefore, even when image output is performed for a long time in a high-temperature, high-humidity environment after being stored in harsh environments, toner agglomeration is less likely to occur.

[0029] On the other hand, (1-2) above is influenced by the resin composition near the surface of the toner particles and the orientation state of the resin. The toner particles are strongly affected. The standard value of ester group ionic fragments near the surface of the toner particles has one or more peaks, which suppresses the seepage of hydrocarbon wax from inside the toner particles due to differences in polarity when stored in harsh environments. In addition, the presence of these peaks means that the ester group concentration on the surface of the toner particles is lower than the ester group concentration in the region 100 nm inside the surface of the toner particles. Therefore, the effect of reducing the affinity between the polydimethylsiloxane of the silica fine particles and the surface of the toner particles, as described in (1-1), can also be expected. As a result, toner aggregates are less likely to form even when images are output for a long time in a high temperature and high humidity environment after being stored in a harsh environment.

[0030] As described above, only by satisfying conditions (1-1) and (1-2) can image defects caused by toner agglomeration be suppressed, even when images are printed for extended periods in a high-temperature, high-humidity environment after being stored in a harsh environment.

[0031] Specifically, to make it difficult for the silica microparticles to adhere to the toner surface, the inorganic microparticles contain silica microparticles surface-treated with polydimethylsiloxane represented by formula (A) and polydimethylsiloxane represented by formula (B). By surface-treating the silica microparticles with polydimethylsiloxane, it is thought that, for example, the polydimethylsiloxane will bond to the silica microparticles and / or the polydimethylsiloxane will be physically adsorbed onto the silica microparticles.

[0032] By treating the silica microparticles with the two types of polydimethylsiloxane described above, it is possible to reduce the amount of trimethylsilanol in the silica microparticles while maintaining a higher polydimethylsiloxane immobilization rate compared to silica microparticles treated only with the polydimethylsiloxane shown in formula (A). This is thought to be due to the high reactivity of the polydimethylsiloxane shown in formula (B) with the silica microparticles. As a result, the polydimethylsiloxane in the silica microparticles can be made less likely to adhere to the surface of the toner particles.

[0033] Furthermore, the polydimethylsiloxane represented by formula (A) does not have reactive functional groups, and therefore has lower polarity than the polydimethylsiloxane represented by formula (B), making it less compatible with the highly polar toner particle surface. For this reason, by using both the polydimethylsiloxane represented by formula (A) and the polydimethylsiloxane represented by formula (B), the generation of trimethylsilanol can be suppressed, and the polarity of the polydimethylsiloxane itself in the silica microparticles can be reduced. This makes it less compatible between the polydimethylsiloxane in the silica microparticles and the highly polar toner particle surface.

[0034] The polydimethylsiloxane in the silica microparticles makes it difficult for them to adhere to the toner particle surface, thus maintaining the shielding properties of the toner particle surface against hydrocarbon wax. As a result, even when stored in harsh environments, the hydrocarbon wax inside the toner particles is less likely to seep out, thus reducing the likelihood of toner agglomeration.

[0035] Furthermore, in the analysis of organic volatile components of silica nanoparticles by headspace method at a heating temperature of 150°C, the total amount of trimethylsilanol in terms of octamethyltrisiloxane, based on the mass of the silica nanoparticles, must be between 1.0 ppm and 5.0 ppm.

[0036] The fact that the amount of trimethylsilanol in the silica microparticles is within the above range means that the amount of trimethylsilanol detached from the polydimethylsiloxane contained in the silica microparticles is small. Therefore, by controlling the amount of trimethylsilanol in the silica microparticles within the above range, the polarity of polydimethylsiloxane can be reduced, making it less likely for polydimethylsiloxane to adhere to the surface of the toner particles. As a result, even when stored in harsh environments, hydrocarbon wax inside the toner particles is less likely to seep out, and toner agglomeration is less likely to occur. Even after being stored in harsh environments and then used for extended periods in high-humidity environments, image defects caused by toner aggregation can be suppressed.

[0037] The total amount of trimethylsilanol in silica microparticles, calculated as octamethyltrisiloxane based on the mass of the silica microparticles, is preferably 1.1 ppm to 3.0 ppm, and more preferably 1.2 ppm to 2.5 ppm. The total amount of trimethylsilanol in silica microparticles can be controlled by the type of treatment agent used for hydrophobizing the surface of the silica microparticles, the amount of the treatment agent, and the particle size of the silica microparticles.

[0038] If the total amount of trimethylsilanol in the silica microparticles is less than 1.0 ppm, it indicates that the number of treatments with polydimethylsiloxane is too small, or that the polydimethylsiloxane in the silica microparticles is the polydimethylsiloxane represented by formula (B). The polydimethylsiloxane represented by formula (B) has reactive functional groups at its ends and side chains, so it is highly reactive with the silica base material, and the amount of polydimethylsiloxane that migrates when the silica microparticles come into contact with various materials decreases. Here, the polydimethylsiloxane contained in the silica microparticles reduces the adhesion between the toner and the various materials by having a portion of the polydimethylsiloxane migrate from the toner to the various materials when they come into contact with the various materials.

[0039] However, if the number of polydimethylsiloxane treatment areas is too small, or if only the highly reactive polydimethylsiloxane represented by formula (B) is used, the amount of polydimethylsiloxane transferred when the silica fine particles come into contact with various materials decreases, thus increasing the adhesion between the toner and the various materials. As a result, toner aggregates are more likely to form when stored in a harsh environment and then used for a long period in a high-temperature, high-humidity environment. In the case of a single-component developer, the generated toner aggregates remain in the friction area between the toner carrier and the charge-applying material, causing image defects (vertical streaks in halftone images).

[0040] Furthermore, if the total amount of trimethylsilanol in the silica microparticles is greater than 5.0 ppm, the polydimethylsiloxane in the silica microparticles becomes polar, making it easier for the polydimethylsiloxane to adhere to the surface of the toner particles. As a result, the shielding effect that suppresses the leaching of hydrocarbon wax from inside the toner due to the polarity of the toner particle surface is reduced, making it easier for hydrocarbon wax to leach out from inside the toner particles when stored in harsh environments.

[0041] When the toner particle surface is measured from the surface down to a depth of 100 nm using time-of-flight secondary ion mass spectrometry, and the ion amount of the structure shown in equation (C) below is counted and divided by the total ion amount, the standard value must be obtained by dividing this value by the total ion amount. It is necessary that at least one peak of the standard value exists within 100 nm of the toner particle surface. Furthermore, when the maximum value among the standard value peaks is taken as A(dmax), and the standard value at the toner particle surface (i.e., depth 0 nm) is taken as A(0), it is necessary that equations (1) and (2) below are satisfied. 1.05≦A(dmax) / A(0)≦5.00 (1) A(0)≧0.010 ···(2) [ka]

[0042] By controlling the area near the toner particle surface (the region from the toner particle surface to a depth of 100 nm) to satisfy equation (1), a certain amount of ester is produced inside the toner particle surface. This allows for the presence of polypropylene groups. In other words, it means that there is more highly polar polyester resin slightly inside the toner particle surface than on the toner particle surface, which can suppress the leaching of hydrocarbon wax from inside the toner even when stored in harsh environments.

[0043] Furthermore, equation (2) indicates that the ester group concentration at the toner particle surface (depth 0m) is above a certain level. By controlling the ester group concentration near the toner particle surface to satisfy equation (2) in addition to satisfying equation (1), a peak in ester group concentration exists near the toner particle surface, and the magnitude of the peak can be kept above a certain level while reducing the ester group concentration present on the toner particle surface.

[0044] By reducing the concentration of ester groups on the toner particle surface, even when silica microparticles contain trimethylsilanol, the silica microparticles and the toner particle surface become less likely to adhere to each other. Furthermore, by ensuring that the peak of ester group concentration near the toner particle surface is above a certain magnitude, the difference in polarity between the vicinity of the toner particle surface and the hydrocarbon wax increases, suppressing the leakage of hydrocarbon wax from inside the toner to the toner particle surface. As a result, image defects caused by toner aggregation can be suppressed even when stored in harsh environments and used for extended periods in high-humidity environments.

[0045] The A(dmax) / A(0) shown in formula (1) is preferably between 1.08 and 2.00, and more preferably between 1.15 and 1.50. If A(dmax) / A(0) is less than 1.05, it means that the ester group concentration at a depth of 0 to 100 nm is not extremely high compared to the ester group concentration on the surface of the toner particles. Therefore, when stored in a harsh environment, the hydrocarbon wax inside the toner cannot be suppressed, and toner aggregates are likely to form.

[0046] Furthermore, if A(dmax) / A(0) is greater than 5.00, it means that ester groups are excessively unevenly distributed in the resin inside the toner surface. To achieve the above range, it is necessary to use resins with extremely high or low physical properties such as molecular weight and acid value, which tends to result in large variations in ester group concentration among toner particles. As a result, when stored in harsh environments, some toners may not be able to suppress the leaching of hydrocarbon wax from inside the toner, making toner agglomeration more likely. A(dmax) / A(0) can be controlled by the high-temperature, high-pH treatment process described later, or by the composition of the polar resin on the surface of the toner particles.

[0047] Regarding equation (2), in toners that contain polyester resin within 100 nm of the toner particle surface and satisfy equation (1), a certain amount of the structure represented by equation (C) may exist on the surface of the toner particles (depth 0 nm). Therefore, it is considered difficult to manufacture toners in which A(0) is less than 0.010.

[0048] A(0) is preferably 0.020 or higher, more preferably 0.030 or higher, and even more preferably 0.040 or higher. There is no particular upper limit, but it is preferably 0.100 or lower, more preferably 0.080 or lower, and even more preferably 0.074 or lower. A(0) can be controlled by the high-temperature, high-pH treatment process described later, or by the composition of the polar resin on the surface of the toner particles.

[0049] A(dmax) is preferably 0.040 or higher, more preferably 0.050 or higher. There is no particular upper limit, but it is preferably 0.200 or lower, more preferably 0.120 or lower, and even more preferably 0.100 or lower.

[0050] Measurements were taken from the toner particle surface to a depth of 100 nm using time-of-flight secondary ion mass spectrometry. Furthermore, when the standard value is obtained by dividing the amount of ions in the structure shown in formula (C) by the total amount of ions, and the standard value at a depth of 100 nm from the surface of the toner particle is taken as A(100), it is preferable that the following formula (3) is satisfied. 1.05≦A(dmax) / A(100)≦5.00 (3)

[0051] The above equation (3) satisfies the requirement that the ester group concentration in the region closer to the toner particle surface is above a certain level compared to the resin in the region where hydrocarbon wax is present, which is 100 nm from the surface of the toner particle. Because the ester group concentration near the toner particle surface is above a certain level compared to the region inside the toner particle, the hydrocarbon wax inside the toner particle tends to remain inside the toner particle due to the difference in polarity.

[0052] Therefore, it is possible to suppress the hydrocarbon wax inside the toner particles from seeping out onto the toner surface. As a result, even when stored in a harsh environment and used for a long period of time in a high-humidity environment, image defects caused by toner agglomeration can be suppressed. A(dmax) / A(100) is more preferably 1.10 or higher, and even more preferably 1.20 or higher. On the other hand, the upper limit is more preferably 3.00 or lower, and even more preferably 2.00 or lower.

[0053] A(dmax) / A(100) can be controlled by the high-temperature, high-pH treatment process described later and by the composition of the polar resin on the surface of the toner particles. A(100) is preferably 0.030 or higher, and more preferably 0.040 or higher. There is no particular upper limit, but it is preferably 0.200 or lower, more preferably 0.100 or lower, and even more preferably 0.080 or lower.

[0054] The inventors believe that the mechanism by which the ester group represented by formula (C) above can be unevenly distributed near the surface of toner particles is as follows: It is possible to control this by designing the structure represented by formula (C) in a way that takes into account the state of existence of the structure, such as unevenly distributing monomer units having nonpolar groups and monomer units having polar groups within the polyester molecule, so that it has a specific compositional distribution.

[0055] As a specific method, the distribution of ester bond sites in the polyester resin can be controlled by aligning the orientation of the terminal carboxylic acid groups of the polar polyester resin near the surface of the toner particles, or by using polymers with compositions that have significantly different polarity distributions in combination. Furthermore, for example, by treating toner particles containing a polyester resin containing the structure shown in formula (C) in an aqueous medium with a pH and heat above a certain level, the ester bond sites in the polyester resin become more easily migrated to the surface of the toner particles. On the other hand, because the polyester resin containing the structure shown in formula (C) has a distribution of ester bond sites, a distribution of orientation states also occurs, and it is thought that the structure shown in formula (C) can be concentrated in the region within a depth of 100 nm from the surface of the toner particles.

[0056] <Silica microparticles> The following describes silica nanoparticles. As mentioned above, the silica nanoparticles are surface-treated with polydimethylsiloxanes represented by formulas (A) and (B). Furthermore, it is preferable that the silica nanoparticles are surface-treated with polydimethylsiloxanes represented by formula (A) and polydimethylsiloxanes represented by formula (D). In other words, it is preferable that the polydimethylsiloxane represented by formula (B) is the polydimethylsiloxane represented by formula (D). [ka]

[0057] In the formula, R 1 R is a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, an alkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), or a hydrogen atom. 2 is a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom. Preferably R 1 and R 2 These are, respectively, a carbinol group, a hydroxyl group, or a hydrogen atom. The methyl group in the side chain of formula (B) may be substituted with a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom. n, m, and p are the average number of repeating units, where n is 30 to 200 (preferably 40 to 100, more preferably 50 to 80), m is 30 to 200 (preferably 40 to 100, more preferably 50 to 80), and p is 30 to 200 (preferably 40 to 100, more preferably 50 to 80).

[0058] By treating silica microparticles with two types of polydimethylsiloxanes, formulas (A) and (D), the amount of trimethylsilanol in the silica microparticles can be reduced compared to silica microparticles treated with polydimethylsiloxanes represented by formulas (A) and (B). This is due to the high reactivity of the polydimethylsiloxane represented by formula (D) with the silica base material. As a result, the polydimethylsiloxane in the silica microparticles does not adhere well to the toner surface. Consequently, toner agglomeration is less likely to occur even after storage in harsh environments and long-term use in high-temperature, high-humidity environments.

[0059] The number-average particle size of the primary particles of the silica microparticles is preferably between 5 nm and 30 nm, and more preferably between 6 nm and 12 nm. By controlling the number-average particle size of the primary particles of the silica microparticles within the above range, the fluidity of the toner can be significantly improved when silica microparticles are added. As a result, image defects caused by toner aggregation can be suppressed even when stored in a harsh environment and used for a long period of time in a high-temperature, high-humidity environment.

[0060] Examples of raw silica fine particles include both dry silica, which is produced by the vapor phase oxidation of silicon halogen compounds and is also called fumed silica, and wet silica, which is manufactured from water glass or the like. Dry silica is preferred because it has fewer silanol groups on its surface and inside and no manufacturing residue.

[0061] The polydimethylsiloxanes represented by formulas (A), (B), and (D) are preferably highly volatile so that they can be efficiently evaporated and removed by the surface treatment described later. For this reason, polydimethylsiloxanes with relatively small molecular weights are preferred.

[0062] The molecular weight of the polydimethylsiloxane represented by formulas (A), (B), and (D) is preferably 250 to 50,000, more preferably 250 to 10,000, and even more preferably 250 to 5,000, as a number-average molecular weight. When the molecular weight of the polydimethylsiloxane is 50,000 or less, its volatility is moderate, making it easier to efficiently evaporate and remove it in the surface treatment described later, and to react with the silica base material. On the other hand, when the molecular weight of the polydimethylsiloxane is 250 or more, it becomes easier to impart high hydrophobicity.

[0063] From the viewpoint of uniform treatment, it is preferable to use the polydimethylsiloxane represented by formulas (A), (B), and (D) diluted in a suitable solvent to, for example, about 5 to 50% by mass for surface treatment. Examples of solvents include hexane, toluene, alcohol (aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, and propanol), acetone, or water or a mixture of two or more of these.

[0064] The amount of polydimethylsiloxane used for surface treatment of silica fine particles varies depending on the type of silica raw material (specific surface area, etc.), the type of polydimethylsiloxane (molecular weight, etc.), etc., and is not particularly limited. Typically, the amount is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, and even more preferably 5 to 30 parts by mass per 100 parts by mass of silica fine particles. If the amount of polydimethylsiloxane used is above the lower limit, sufficient surface treatment can be performed, and silica fine particles with high hydrophobicity can be obtained. On the other hand, if polydimethylsiloxane below the upper limit is used, the hydrophobicity of the silica fine particles can be increased and aggregation can be reduced.

[0065] The amount of surface treatment for the polydimethylsiloxane represented by formula (A) is preferably 3 to 40 parts by mass, more preferably 5 to 35 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of silica fine particles before surface treatment. The amount of surface treatment for the polydimethylsiloxane represented by formula (B) is preferably 1 to 35 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of silica fine particles before surface treatment.

[0066] In the surface treatment, the mass ratio (B) / (A) of polydimethylsiloxane represented by formula (B) to polydimethylsiloxane represented by formula (A) is preferably 0.05 to 10.00, more preferably 0.06 to 6.00, and even more preferably 0.20 to 1.00.

[0067] (Surface treatment method) The surface treatment method is preferably carried out in an inert gas atmosphere such as a nitrogen atmosphere to prevent hydrolysis and oxidation. Specifically, the silica is placed in a container equipped with a stirring device such as a Henschel mixer. The method involves adding the silica raw material, stirring under nitrogen purge, spraying a diluted solution of polydimethylsiloxane to mix with the silica raw material, and then heating to initiate the reaction. The spraying may be performed prior to heating, or while heating to the treatment temperature or a lower temperature.

[0068] (Processing conditions) The surface treatment involves applying a predetermined amount of polydimethylsiloxane to the silica material and heating it under stirring to react with and immobilize the polydimethylsiloxane on the surface of the silica material. Here, the polydimethylsiloxane may be diluted with the various solvents mentioned above before being applied to the silica material.

[0069] The heating temperature in this surface treatment varies depending on the reactivity of the polydimethylsiloxane used, but is preferably 150 to 380°C, more preferably 250 to 350°C. The treatment time also varies depending on the heating temperature and the reactivity of the polydimethylsiloxane used, but is preferably 5 to 300 minutes, more preferably 50 to 200 minutes, and even more preferably 80 to 160 minutes.

[0070] The surface treatment temperature and time allow polydimethylsiloxane to react sufficiently with the silica raw material, resulting in good hydrophobicity of the silica fine particles. Furthermore, production efficiency is also improved.

[0071] It is preferable to first hydrophobize the silica raw material using a polydimethylsiloxane represented by formula (A), which is excellent at hydrophobizing the silica raw material, and then treat it with a polydimethylsiloxane represented by formula (B) or (D). By treating in the above order, the amount of trimethylsilanol remaining in the silica fine particles can be reduced, and silica fine particles with high hydrophobicity can be obtained.

[0072] From the viewpoint of improving fluidity and chargeability, the silica fine particle content is preferably 0.1 parts by mass to 4.0 parts by mass, more preferably 0.2 parts by mass to 3.5 parts by mass, and even more preferably 0.7 parts by mass to 1.5 parts by mass, per 100 parts by mass of toner particles. The toner may also have inorganic fine particles other than the silica fine particles described above on the surface of the toner particles. Examples of inorganic fine particles include titanium oxide particles, alumina particles, or complex oxide particles thereof.

[0073] <Binding resin> The toner particles contain a binder resin. The binder resin is not particularly limited and any known resin can be used. Examples include: vinyl resins using polymerizable monomers, polyester resins, polyol resins, polyvinyl chloride resins, phenol resins, naturally modified phenol resins, naturally modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone indene resins, and petroleum resins. Preferably, the resin is a vinyl resin, a polyester resin, a mixture of polyester resin and vinyl resin, or a hybrid resin in which both are partially reacted.

[0074] <Polyester resin> The binder resin preferably contains a polyester resin. The polyester resin will be described below. The polyester resin is not particularly limited, but it is preferably an amorphous polyester resin, and examples include the following.

[0075] Examples of divalent acid components include the following dicarboxylic acids or their derivatives: benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or their anhydrides or lower alkyl esters; succinic acid, adipic acid, sebacic acid, and azelaic acid. Alkyl dicarboxylic acids such as n-dodecenyl succinic acid, n-dodecyl succinic acid, alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid, or their anhydrides or lower alkyl esters; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or their anhydrides or lower alkyl esters.

[0076] Examples of dihydric alcohol components include: ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol (CHDM), hydrogenated bisphenol A, bisphenol and its derivatives.

[0077] In addition to the divalent carboxylic acid compounds and divalent alcohol compounds mentioned above, the polyester resin may also contain monovalent carboxylic acid compounds, monovalent alcohol compounds, trivalent or higher carboxylic acid compounds, and trivalent or higher alcohol compounds as constituent components.

[0078] Examples of monovalent carboxylic acid compounds include aromatic carboxylic acids with 30 or fewer carbon atoms, such as benzoic acid and p-methylbenzoic acid, and aliphatic carboxylic acids with 30 or fewer carbon atoms, such as stearic acid and behenic acid. Examples of monovalent alcohol compounds include aromatic alcohols with 30 or fewer carbon atoms, such as benzyl alcohol, and aliphatic alcohols with 30 or fewer carbon atoms, such as lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol.

[0079] The carboxylic acid compound with a valency of 3 or more is not particularly limited, and examples thereof include trimellitic acid, trimellitic anhydride, pyromellitic acid, etc. Further, examples of the alcohol compound with a valency of 3 or more include trimethylolpropane, pentaerythritol, glycerin, etc.

[0080] The polyester resin preferably contains a monomer unit represented by the following formula (E), a monomer unit represented by the formula (F), and a monomer unit represented by the formula (G). A monomer unit refers to the form in which monomer substances in the polymer have reacted. The content ratio of the monomer unit represented by the formula (E) in the polyester resin is preferably 30% by mass or more and 50% by mass or less, and more preferably 40% by mass or more and 50% by mass or less. The content ratio of the monomer unit represented by the formula (F) in the polyester resin is preferably 25% by mass or more and 50% by mass or less, and more preferably 30% by mass or more and 45% by mass or less. The content ratio of the monomer unit represented by the formula (G) in the polyester resin is preferably 0.4% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and even more preferably 6% by mass or more and 25% by mass or less.

[0081] In the formula, R 3 represents a benzene ring, and is preferably bonded at the para position. R 4 each represents an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10. R 5 represents an ethylene group or a propylene group, and is preferably an ethylene group.

Chemical formula

[0082] [[ID=..]] The inventors believe that by controlling the content ratio of monomer units in the polyester resin within the above range, it becomes easier to increase the concentration of ester groups in the polyester resin and to align the orientation of carboxylic acid groups at the polymer ends. In other words, a polyester resin in which the content ratio of monomer units is controlled within the above range contains a certain amount of monomer units represented by formula (G) with a low molecular weight, thus increasing the concentration of ester groups in the polyester resin. Furthermore, because it contains a certain amount of monomer units represented by formula (G) with a low molecular weight, its flexibility can be increased. The inventors believe that by increasing the concentration of ester groups in the polyester resin and increasing the flexibility of the polyester resin, it becomes easier to align the orientation of carboxylic acid groups at the polymer ends by utilizing the polarity of the ester groups.

[0083] As a result, the concentration of ester groups near the surface of toner particles can be easily controlled to the range of formulas (1) and (2) above, and image defects caused by toner agglomeration can be suppressed even when the product is stored in a harsh environment and then used for a long period of time in a high-humidity environment.

[0084] The polyester resin preferably contains monomer units represented by the following formula (H). [ka]

[0085] By including a monomer unit formed by polymerizing isosorbide represented by the above formula (H) in the polyester resin, the polarity of the polyester resin can be optimized, and the polyester resin This makes it easier to unevenly distribute monomer units with nonpolar groups and monomer units with polar groups within the unit.

[0086] The inventors believe the reason for this is as follows: Since the monomer unit represented by formula (H) has an ether bond in its cyclic structure, it can moderately mitigate the influence of the ester group component on the polarity of each unit compared to monomer units with ether bonds such as ethylene glycol. Furthermore, since the monomer unit represented by formula (H) has a cyclic structure with the oxygen atom facing outward, it is easier to utilize the polarity derived from the cyclic structure to unevenly distribute the polar group compared to monomer units containing alkyl chains in the main chain such as ethylene glycol. For this reason, the inventors believe that it is possible to moderately impart polarity due to the ester group component to the polyester resin, and to unevenly distribute alcohol monomer units having polar groups represented by formulas (G) and (H) and alcohol monomer units having non-polar groups represented by formula (F). As a result, it becomes easier to control the ester group concentration near the surface of the toner particles within the range of formulas (1) and (2) above, and even when stored in a harsh environment and used for a long period in a high-humidity environment, image defects caused by toner agglomeration can be suppressed.

[0087] The content of the monomer unit represented by the above formula (H) in the polyester resin is preferably 1.0% by mass or more and 4.0% by mass or less, and more preferably 2.0% by mass or more and 3.5% by mass or less.

[0088] The weight-average molecular weight of the polyester resin is preferably 6,000 to 20,000, and more preferably 9,000 to 15,000. The acid value of the polyester resin is preferably 3.0 to 15.0 mgKOH / g, and more preferably 4.0 to 10.0 mgKOH / g. There are no particular restrictions on the method for producing the polyester resin, and known methods can be used.

[0089] (polymerizable monomer) The binder resin may contain a vinyl resin. As the polymerizable monomer capable of producing a vinyl resin, a vinyl monomer capable of radical polymerization is used. As the vinyl monomer, a monofunctional monomer or a polyfunctional monomer can be used.

[0090] Examples of monofunctional monomers include styrene; styrene derivatives such as α-methylstyrene, β-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-phenylstyrene; acrylic polymerizable monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate; methacrylic polymerizable monomers such as methyl methacrylate, ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

[0091] The polymerizable monomer preferably contains styrene or a styrene derivative and an acrylic polymerizable monomer. That is, the binder resin preferably contains a styrene-acrylic resin. The styrene-acrylic resin is a polymer of monomers containing at least one selected from the group consisting of styrene and styrene derivatives, and at least one selected from the group consisting of acrylic polymerizable monomers and methacrylic polymerizable monomers. The styrene-acrylic resin preferably contains styrene and an acrylic polymerizable monomer and a methacrylic polymerizable monomer. It is a polymer of monomers containing at least one selected from the group.

[0092] Examples of polyfunctional monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, and divinyl ether.

[0093] Crosslinking agents can also be used with polymerizable monomers. Specifically, compounds having two or more polymerizable double bonds can be used. Examples include carboxylic acid esters having two double bonds, such as propylene glycol diacrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, and 1,3-butanediol dimethacrylate; aromatic divinyl compounds, such as divinylbenzene and divinylnaphthalene; divinyl compounds, such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. From the viewpoint of achieving both low-temperature fixability and improved high-temperature elasticity, it is preferable to use carboxylic acid esters. These crosslinking agents can be used alone or in combination.

[0094] The amount of crosslinking agent added is preferably 0.01 parts by mass or more and 5.00 parts by mass or less per 100 parts by mass of polymerizable monomer or binder resin that produces the binder resin, and more preferably 0.10 parts by mass or more and 3.00 parts by mass or less.

[0095] Polymerization initiators may be used in the production of toner particles. Oil-soluble initiators and / or water-soluble initiators are used as polymerization initiators. Preferably, the initiator has a half-life of 0.5 to 30 hours at the reaction temperature during the polymerization reaction. Furthermore, when the polymerization reaction is carried out with an addition amount of 0.5 to 20 parts by mass per 100 parts by mass of polymerizable monomer, a polymer having a maximum molecular weight between 10,000 and 100,000 is usually obtained, and toner particles with appropriate strength and melting properties can be obtained, which is therefore preferable.

[0096] Examples of polymerization initiators include azo-based or diazo-based polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile; and peroxide-based polymerization initiators such as benzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. To control the degree of polymerization of polymerizable monomers, it is also possible to add and use known chain transfer agents, polymerization inhibitors, etc.

[0097] <Core-shell structure> Toner particles preferably have a core-shell structure comprising core particles and a shell on the surface of the core particles. Preferably, the core particles contain styrene-acrylic resin and the shell contains polyester resin. Having a core-shell structure as described above makes it difficult for hydrocarbon wax contained inside the toner particles to seep out onto the surface of the toner particles. This is because hydrocarbon wax has a higher affinity for the styrene-acrylic resin of the core particles than for the polyester resin of the shell, so even when stored in a harsh environment, the hydrocarbon wax inside the toner tends to remain in the styrene-acrylic resin of the core particles. As a result, even when stored in a harsh environment and used for a long period in a high-humidity environment, image defects caused by toner agglomeration can be suppressed.

[0098] In cross-sectional observation of toner using a transmission electron microscope, the average thickness of the shell is preferably between 100 nm and 200 nm, and more preferably between 105 nm and 160 nm. By having the shell thickness of the toner particles within this range, the polyester resin contained in the shell can further suppress the leaching of hydrocarbon wax. As a result, image defects caused by toner agglomeration can be suppressed even after storage in harsh environments and long-term use in high-humidity environments.

[0099] The toner may also be in the following form: A toner containing toner particles containing styrene-acrylic resin, polyester resin, and hydrocarbon wax, and inorganic fine particles, The inorganic fine particles contain silica fine particles surface-treated with polydimethylsiloxane represented by formula (A) and polydimethylsiloxane represented by formula (B). The toner particles have a core particle and a shell on the surface of the core particle, The core particles have the styrene-acrylic resin, The shell has the polyester resin, In cross-sectional observation of the toner using a transmission electron microscope, the average thickness of the shell is between 100 nm and 200 nm. When the toner particles are measured from the surface to a depth of 100 nm using time-of-flight secondary ion mass spectrometry, and the ion amount of the structure shown in formula (C) above is divided by the total ion amount counted, the standard value is defined as follows: Within a range of 100 nm from the surface of the toner particles, there is one or more peaks of the specified value. When the maximum value among the peaks of the specified value is defined as A(dmax), and the specified value on the surface of the toner particles is defined as A(0), A toner characterized by satisfying the following formulas (1) and (2). 1.05≦A(dmax) / A(0)≦5.00 (1) A(0)≧0.010 ···(2)

[0100] <Hydrocarbon wax> Hydrocarbon waxes are preferably aliphatic hydrocarbon waxes. Examples include low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, paraffin wax, and polyolefin wax. These waxes may be used individually or in combination of two or more.

[0101] Furthermore, antioxidants may be added to these hydrocarbon waxes to the extent that they do not affect the above effects. The hydrocarbon wax content is preferably 1.0 part by mass to 30.0 parts by mass, and more preferably 5.0 parts by mass to 15.0 parts by mass, per 100.0 parts by mass of the binder resin. The melting point of the hydrocarbon wax is preferably 30°C to 120°C, and more preferably 60°C to 100°C.

[0102] <Coloring agent> Known pigments and dyes can be used as colorants. Pigments are preferred as colorants due to their excellent weather resistance. Examples of cyanide-based colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, the following can be mentioned: CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

[0103] Magenta-based colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, and benz Examples include imidazolon compounds, thioindigo compounds, and perylene compounds. Specifically, the following are examples: CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254, and CI Pigment Violet 19.

[0104] Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following are examples: CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191, and 194.

[0105] Examples of black colorants include carbon black and those colored black using the above-mentioned yellow, magenta, and cyan colorants. These colorants may be used individually or as a mixture of two or more. Furthermore, they can be used in a solid solution state. The colorant content is preferably 1.0 part by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the binder resin.

[0106] <Method for manufacturing toner particles> Toner particles can be manufactured using any of the known methods, including dry polymerization, emulsion polymerization, dissolution-suspension polymerization, and suspension polymerization. To control the presence of formula (C) near the surface of the toner particles within a specific range, it is preferable to perform the following processing steps.

[0107] The toner particles obtained in each manufacturing method are dispersed in an aqueous medium, and the process involves treating the medium at a temperature of 90°C or higher with pH(1) followed by treatment with pH(2). pH(1) and pH(2) preferably satisfy the following formulas (4) and (5). (Hereinafter referred to as the high-temperature, high-pH treatment process.) pH(1) <pH(2) ···(4) 5.5 ≤ pH(2) ≤ 11.0 ···(5)

[0108] This high-temperature, high-pH treatment process is thought to orient the terminal carboxylic acids contained in the polyester resin toward the toner particle surface, thereby allowing the ester bond sites to be concentrated near the toner particle surface. As a result, the orientation state of formula (C) can be controlled more precisely, making it easier to concentrate the ester bond sites within 100 nm of the toner particle surface. Furthermore, the material selectivity, such as that of polyester resin, is also improved.

[0109] The temperature is preferably 95°C or higher. The upper limit is not particularly limited, but for example, 110°C or lower, 105°C or lower, and 100°C or lower are preferred. Performing the treatment at a higher temperature of 90°C or higher within the above pH range makes it easier to change the orientation state of the molecules in the polyester resin. In formula (5), by making pH(2) greater than pH(1), it is possible to easily change the orientation state of the polyester resin immobilized in the resulting toner particles.

[0110] Specifically, by setting the pH(2) to 5.5 or higher in equation (5), the carboxylic acid at the ends of the polyester resin becomes more susceptible to acid dissociation. This allows the carboxylic acid end of the polyester resin to selectively orient towards the toner particle surface, making it easier to control the orientation more precisely. Furthermore, by setting the pH(2) to 11.0 or lower, the generation of bubbles, which tend to cause the formation of coarse particles, is suppressed, and manufacturing can be carried out without quality concerns such as fogging due to charging defects caused by the generated coarse particles.

[0111] pH(2) is more preferably 6.0 to 10.5. pH(1) is preferably 3.0 or higher and less than 5.5, more preferably 4.5 or higher and less than 6.0. The treatment time at pH(1) is preferably 5 minutes to 6 hours, more preferably 30 minutes to 3 hours. The treatment time at pH(2) is preferably 1 minute to 120 minutes, more preferably 10 minutes to 60 minutes.

[0112] When toner particles are produced in an aqueous medium, such as by suspension polymerization or emulsification agglutination, a suspension in which toner particles are dispersed in the aqueous medium is obtained, and it is preferable to perform the above-mentioned high-temperature, high-pH treatment using this suspension. When toner particles are produced by a dry method, such as by grinding, it is preferable to re-slurry the obtained toner particles to obtain a suspension and then go through the above-mentioned high-temperature, high-pH treatment step.

[0113] It is preferable that the toner particles be produced by a suspension polymerization method, in which a polymerizable monomer composition is granulated in an aqueous medium to form particles of the polymerizable monomer composition. The method for producing toner particles includes a granulation step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, a hydrocarbon wax, and a polyester resin in an aqueous medium, and a polymerization step of obtaining toner particles by polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. After the polymerization step, it is preferable to perform a high-temperature, high-pH treatment step on the obtained toner particles. The toner particles obtained in this manner can be filtered, washed, and dried by known methods to obtain toner particles.

[0114] The following describes in detail a method for producing toner particles using the grinding method. Examples of manufacturing methods for toner particles using the grinding method are as follows: In the raw material mixing process, binder resin, hydrocarbon wax, and other additives as needed are weighed in predetermined amounts, blended, and mixed to form the toner particles. Examples of mixing equipment include double-con mixers, V-type mixers, drum-type mixers, super mixers, FM mixers, Nauter mixers, and Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.).

[0115] Next, the mixed materials are melt-kneaded to disperse hydrocarbon waxes and the like in the binder resin. In the melt-kneading process, batch-type kneaders such as pressure kneaders and Banbury mixers, or continuous-type kneaders can be used. Due to the advantage of being able to produce continuously, single-screw or twin-screw extruders are the mainstream. Examples include the KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), the TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), the PCM kneader (manufactured by Ikegai Co., Ltd.), the twin-screw extruder (manufactured by KCK Co., Ltd.), the Co-kneader (manufactured by Buss Co., Ltd.), and the Needex (manufactured by Nippon Coke Industries Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water in a cooling process.

[0116] Next, the cooled resin composition is pulverized to the desired particle size in a pulverization process. In the pulverization process, the material is coarsely pulverized using a pulverizer such as a crusher, hammer mill, or feather mill, and then further finely pulverized using a fine pulverizer such as a Kryptron system (manufactured by Kawasaki Heavy Industries), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Freund Turbo Co., Ltd.), or an air jet type pulverizer.

[0117] Subsequently, the toner particles are obtained by classifying or sieving them as needed using classifiers or sieving machines such as the inertial classifier Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), the centrifugal classifier Turboplex (manufactured by Hosokawa Micron Corporation), the TSP separator (manufactured by Hosokawa Micron Corporation), and the Faculty (manufactured by Hosokawa Micron Corporation).

[0118] The obtained toner particles are preferably subjected to reslurrying and the aforementioned high-temperature, high-pH treatment. Then, toner particles can be obtained by filtering, washing, and drying using known methods.

[0119] The following provides a detailed explanation of a toner particle manufacturing method using the emulsification and agglutination method as an example. (Preparation process of binder resin particle dispersion) A dispersion of binder resin particles can be prepared, for example, as follows: If the binder resin is a homopolymer or copolymer of vinyl monomers (vinyl resin), a dispersion can be prepared by dispersing vinyl resin particles in an ionic surfactant by emulsion polymerization or seed polymerization of the vinyl monomers in an ionic surfactant.

[0120] If the binder resin is a resin other than a vinyl-based resin such as polyester resin, the resin is mixed with an aqueous medium containing an ionic surfactant or a polymer electrolyte. Then, this solution is heated to a temperature above the melting or softening point of the resin to dissolve it, and a dispersion is prepared in which the binder resin particles are dispersed in the ionic surfactant using a disperser with strong shear force, such as a homogenizer.

[0121] There are no particular restrictions on the means of dispersion, but examples include known dispersion devices such as rotary shear homogenizers, ball mills with media, sand mills, and dyno mills. Furthermore, a phase inversion emulsification method may be used as a method for preparing the dispersion. The phase inversion emulsification method involves dissolving the binder resin in an organic solvent, adding a neutralizing agent and dispersion stabilizer as needed, adding an aqueous solvent dropwise under stirring to obtain emulsion particles, and then removing the organic solvent from the resin dispersion to obtain an emulsion. At this time, the order in which the neutralizing agent and dispersion stabilizer are added may be changed.

[0122] In the emulsification and agglutination method, a dispersion of colorant particles may be used as needed. The dispersion of colorant particles consists of at least colorant particles dispersed in a dispersant. In the emulsification and agglutination method, a dispersion of wax particles is used. The dispersion of wax particles consists of at least hydrocarbon wax dispersed in a dispersant.

[0123] (Agglutination process) The agglomeration step for forming aggregated particles is a step in which aggregated particles containing binder resin particles, hydrocarbon wax particles, and optionally added colorant particles are formed in an aqueous medium containing binder resin particles, hydrocarbon wax particles, and optionally added colorant particles.

[0124] (fusion process) The fusion process involves heating and fusing the resulting aggregated particles. Before entering the fusion process, pH adjusters, polar surfactants, nonpolar surfactants, etc., can be added as appropriate to prevent fusion between toner particles.

[0125] The heating temperature should be above the glass transition temperature of the resin contained in the aggregated particles (or the glass transition temperature of the resin with the highest glass transition temperature if there are two or more types of resin) and below the decomposition temperature of the resin. Therefore, the heating temperature varies depending on the type of resin in the binder resin particles and cannot be specified in general terms, but generally it is above the glass transition temperature of the resin contained in the aggregated particles and 140°C or less. Heating can be carried out using heating devices and equipment that are known in themselves.

[0126] The fusion time depends on the heating temperature; a higher temperature requires a shorter time, while a lower temperature requires a longer time. In other words, the fusion time cannot be precisely defined as it depends on the heating temperature, but it is generally between 30 minutes and 10 hours.

[0127] Toner particles are obtained by performing the above-described dispersion preparation, aggregation, and fusion steps. The obtained toner particles are then filtered, washed, and dried using known methods. The process can then proceed to subsequent steps such as drying. It is preferable to perform high-temperature, high-pH treatment on the obtained toner particles. After that, the toner particles can be obtained by filtering, washing, and drying using known methods.

[0128] Toner can be obtained by externally mixing inorganic fine particles, including silica fine particles, with the obtained toner particles using a known method. A known mixer, such as an FM mixer (manufactured by Nippon Coke Co., Ltd.), can be used for the external mixing.

[0129] <Various measurement methods> The following describes various measurement methods, etc. <Method for measuring the amount of trimethylsilanol in silica microparticles using the headspace method> The amount of trimethylsilanol in silica microparticles is measured using silica microparticles separated from toner. (Method for separating silica microparticles from the toner surface) When using silica microparticles separated from the toner surface as the measurement sample, the separation of silica microparticles from the toner is performed using the following procedure. Furthermore, toner particles with the external additive removed can also be obtained using the separation method described below, and these obtained toner particles can be used in each measurement method.

[0130] (In the case of non-magnetic toner) Add 160g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100mL of deionized water and dissolve it over a water bath to prepare a concentrated sucrose solution. Place 31g of this concentrated sucrose solution and 6mL of Contaminon N (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) into a centrifuge tube to prepare a dispersion. Add 1g of toner to this dispersion and break up any clumps of toner with a spatula or similar tool.

[0131] The centrifugation tube is placed in an Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX) and shaken for 20 minutes at a rate of 350 strokes per minute. After shaking, the solution is transferred to a 50 mL glass tube for the swing rotor and centrifuged in a centrifuge at 3500 rpm for 30 minutes.

[0132] After centrifugation, toner particles are present in the uppermost layer of the glass tube, while silica microparticles are present in the lower aqueous solution. The lower aqueous solution is collected, and centrifugation is repeated as needed to ensure sufficient separation. After drying the dispersion, the silica microparticles are collected. The upper layer of toner particles is collected, filtered, and washed with 2 liters of deionized water heated to 40°C. The washed toner particles are then removed.

[0133] (In the case of magnetic toner) A dispersion medium is prepared by adding 6 mL of Contaminon N (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) to 100 mL of deionized water. 5 g of toner is added to this dispersion medium and dispersed for 5 minutes using an ultrasonic disperser (AS ONE Corporation VS-150). After that, it is set in an Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX) and shaken for 20 minutes at a rate of 350 reciprocations per minute.

[0134] Next, the toner particles are restrained using a neodymium magnet. Since silica microparticles are present in the upper aqueous solution, the upper aqueous solution is collected, and magnetic separation is repeated as needed. After sufficient separation, the dispersion is dried, and the silica microparticles are collected. The toner particles restrained using the neodymium magnet are also collected. These toner particles are washed with 2 liters of deionized water heated to 40°C, and the washed toner particles are removed.

[0135] (Measurement of trimethylsilanol content in silica microparticles) The trimethylsilanol content in silica microparticles is obtained by performing organic volatile component analysis of the silica microparticles at a heating temperature of 150°C using the headspace method, and calculating the concentration in terms of octamethyltrisiloxane based on the mass of the silica microparticles. The measurement conditions are shown below.

[0136] The measurement was performed using the multiple headspace extraction method. This method involves placing the sample in a sealed container of a predetermined volume, heating the container as needed, and extracting the gas phase from within the container. The headspace sampler used was a PerkinElmer HS40XL, and the GC / MS was a ThermoQuest TRACE GC / TRACE MS. The sample vial was connected to a gas chromatograph.

[0137] (i) Headspace sampler conditions • Sample amount: 500 mg • Sample temperature: 150℃ • Needle temperature: 150℃ Transfer line temperature: 180℃ ·Holding time: 60min • Pressurization time: 0.25 min • Infusion time: 0.08 min

[0138] (ii)GC conditions • Column: HP5-MS (0.25mm, 60m) • Column temperature: Maintain at 40°C for 3 minutes, increase temperature by 2.0°C / min between 40°C and 70°C, increase temperature by 5.0°C / min between 70°C and 150°C, and increase temperature by 10.0°C / min between 150°C and 300°C. • Split ratio 50:1

[0139] (iii) appliances; As a sealed container, we will use a glass vial for headspace analysis manufactured by PerkinElmer Japan Co., Ltd.

[0140] (iv) Method 1) Preparation of standard samples First, as a standard sample of trimethylsilanol, prepare an acetone solution with an octamethyltrisiloxane concentration of 1000 ppm. Place 5 μL of this solution into a glass vial using a 10 μL microsyringe and quickly seal it with a high-temperature analytical septum. 2) Preparation of silica microparticle samples 50 mg of silica microparticles are placed in a glass vial, sealed tightly with a septum for high-temperature analysis, and prepared as a sample.

[0141] (v)Analysis Standard samples of octamethyltrisiloxane solution were measured using quantitative multiple headspace extraction to determine the total peak area per 0.005 μL of octamethyltrisiloxane (note that since GC sensitivity varies between days, the peak area per 0.005 μL of octamethyltrisiloxane must be checked after each measurement). The gaseous component was introduced into a mass spectrometer (mass spectrometer), and the resulting peak was determined to be octamethyltrisiloxane. Confirm that the peak is derived from roxane. Next, silica nanoparticles are measured in the same way as octamethyltrisiloxane, introduced into a mass spectrometer, the trimethylsilanol peak is identified, and the sum of the peak areas is calculated. The amount of trimethylsilanol in the measured sample is calculated proportionally from the peak area of ​​the octamethyltrisiloxane standard sample, and the amount of trimethylsilanol in the silica nanoparticles is obtained.

[0142] <Method for measuring ion quantity (secondary ion mass / secondary ion charge number (m / z)) using time-of-flight secondary ion mass spectrometry (TOF-SIMS)> To determine the concentration distribution of the functional group represented by formula (C) on the surface of toner particles, first, the structure represented by formula (C) is identified in the polar resin, such as polyester resin, of the toner particles. Next, using TOF-SIMS, the ion amount of the monomer unit composed of the acid component is measured among the monomer units composed of the alcohol component and the monomer units composed of the acid component that constitute the above structure (ester bond) represented by formula (C) in the polar resin.

[0143] (1) Identification of the structure shown by formula (C) contained in the polar resin of toner particles. Approximately 1.5 g of toner particles are weighed precisely (X1 [g]) and placed in a pre-weighed cylindrical filter paper (product name: No. 86R, size 28 x 100 mm, manufactured by Advantec Toyo Co., Ltd.) and set in a Soxhlet extractor. Extraction is performed for 18 hours using 200 mL of ethyl acetate as the solvent. During extraction, the reflux rate is maintained so that the solvent extraction cycle is approximately once every 5 minutes. After extraction is complete, the extract is removed, air-dried, and then vacuum-dried at 50°C for 24 hours. Because ethyl acetate has ester groups and is highly polar, it can be used to extract polar resins such as polyester resins that also have ester groups.

[0144] The compositional analysis of the polar resin in toner particles is performed using NMR spectroscopy. Using the dried ethyl acetate extract sample, nuclear magnetic resonance spectroscopy was performed ( 1Perform 1H-NMR [400MHz, CDCl3, room temperature (25°C)]. The analytical conditions are as follows: Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 The composition of the polar resin is analyzed from the NMR spectrum measured using the method described above, and the structure represented by formula (C) contained in the polar resin is identified.

[0145] (2) Measurement of ion quantity using TOF-SIMS For measuring ion quantity (peak intensity) using TOF-SIMS, we use the TRIFT-IV manufactured by ULVAC-PHI. The analysis conditions are as follows: Sample preparation: Apply toner to the indium sheet. Sample pretreatment: None Primary ion: Au ion Acceleration voltage: 30kV Charge neutralization mode: On Measurement mode: Positive Raster: 200 μm Measurement time: 60s

[0146] Typically, TOF-SIMS is a surface analysis technique, and the depth data is approximately 1 nm. Therefore, the intensity inside the toner particles is measured by sputtering the toner particles with argon gas cluster ions and abrading the surface. The sputtering conditions are as follows: Acceleration voltage: 10kV Current: 3.4nA Raster: 600 μm Irradiation time: 5 seconds

[0147] The depth measurement was confirmed beforehand by sputtering a polymethyl methacrylate (PMMA) film under the same conditions to verify the relationship with irradiation time, and it was confirmed that 100 nm could be removed with an irradiation time of 300 s. The ion amount at a depth of 100 nm from the surface of the toner particle is the value of the ion amount measured after 60 sputtering cycles under the above conditions. The ion amount at the surface of the toner particle (depth 0 nm) is the value of the ion amount measured without sputtering the toner particle, using toner particles from which the external additives have been removed using the method described above.

[0148] Calculation and definition of standard value, A(dmax): According to ULVAC-PHIE standard software (Win Cadense), the total count of mass numbers of monomer units composed of the acid component, among the monomer units composed of the alcohol component and the monomer units composed of the acid component that constitute the structure (ester bond) shown by formula (C) in the polar resin identified by compositional analysis, is defined as the ion amount of the structure shown by formula (C) (secondary ion mass / secondary ion charge number (m / z)). The standard value is then defined as the value obtained by dividing this ion amount by the total counted ion amount.

[0149] As mentioned above, the standard value at the outermost surface of the toner particles from which the external additive has been removed is defined as A(0). Furthermore, the process of removing the surface of the toner particles with a 5-second irradiation time under the above sputtering conditions and obtaining the standard value is repeated for a total of 300 seconds (i.e., to a depth of 100 nm), and the standard values ​​from the surface of the toner particles down to a depth of 100 nm are obtained. The standard value at a depth of 100 nm from the surface of the toner particles is defined as A(100).

[0150] Furthermore, among the standard values ​​measured from the toner particle surface up to 100 nm, a standard value that is greater than the values ​​of A(0) and A(100), and that is at least 1.05 times greater than A(0) and A(100), is defined as a peak. The largest peak among the obtained peaks is defined as A(dmax). Therefore, if a standard value has a peak, the number of peaks can range from 1 to 58. A schematic diagram of the analysis results is shown in Figure 2.

[0151] <Method for measuring molecular weight> The molecular weight of resins such as polyester resins is measured by gel permeation chromatography (GPC) as follows: First, the polyester resin is dissolved in tetrahydrofuran (THF) at room temperature. Then, the resulting solution is filtered through a solvent-resistant membrane filter, "Maeshori Disc" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is 0.8% by mass. This sample solution is then measured under the following conditions. Equipment: High-speed GPC system "HLC-8220GPC" [manufactured by Tosoh Corporation] Column: LF-604 double column Eluent:THF Flow rate: 0.6ml / min Oven temperature: 40℃ Sample injection volume: 0.020 ml

[0152] When calculating the molecular weight of the sample, use standard polystyrene resin (for example, product names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-8 A molecular weight calibration curve created using "0, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500" (manufactured by Tosoh Corporation) will be used.

[0153] <Acid value of polyester resin> The acid value is the amount of potassium hydroxide (in mg) required to neutralize the acid contained in 1 g of the sample. The acid value is measured according to JIS K 0070-1992, specifically by following the procedure below.

[0154] Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the above potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titration measuring device AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). 100 ml of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker and titrated with the above potassium hydroxide ethyl alcohol solution. The factor is determined from the amount of potassium hydroxide ethyl alcohol solution required for neutralization. The above 0.100 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0155] The measurement conditions for acid value measurement are shown below. Titration apparatus: Potentiometric titrator AT-510 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) Electrodes: Composite glass electrode double junction type (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) Control software for titration equipment: AT-WIN Titration analysis software: Tview The titration parameters and control parameters during titration are as follows: (Titration parameters) Titration mode: Blank titration Titration method: Total titration Maximum titration volume: 20ml Waiting time before titration: 30 seconds Titration direction: automatic (Control parameters) Endpoint determination potential: 30dE Endpoint determination potential value: 50 dE / dmL End point detection judgment: Do not set Control speed mode: Standard Gain: 1 Data acquisition potential: 4mV Data collection titration volume: 0.1 ml

[0156] For this test, 0.100 g of the sample is accurately weighed into a 250 ml tall beaker, 150 ml of a toluene / ethanol (3:1) mixture is added, and the sample is dissolved over 1 hour. The sample is then titrated using the potassium hydroxide ethyl alcohol solution described above with the potentiometric titrator. Blank test: Perform the titration in the same manner as above, except that no sample is used (i.e., only a mixed solution of toluene / ethanol (3:1) is used). Substitute the obtained results into the following formula to calculate the acid value. A = [(CB) × f × 5.611] / S (In the formula, A: acid value (mgKOH / g), B: volume of potassium hydroxide ethyl alcohol solution added in the blank test (ml), C: volume of potassium hydroxide ethyl alcohol solution added in the main test (ml), f: factor of the potassium hydroxide solution, S: sample (g).)

[0157] <Method for identifying each monomer unit of polyester resin in toner particles and quantifying their content> The above analysis will utilize pyrolysis gas chromatography-mass spectrometry (hereinafter referred to as pyrolysis GC / MS) and NMR. Components with a molecular weight of 1500 or higher will be included in the analysis. This is because the region with a molecular weight of less than 1500 is thought to have a high proportion of wax and contain almost no resin components.

[0158] Pyrolysis GC / MS can determine the constituent monomer units of the total resin in the toner and calculate the peak area of ​​each monomer unit. However, quantitative analysis requires normalization of peak intensity using a reference sample of known concentration. On the other hand, NMR can determine and quantify the constituent monomer units without using a sample of known concentration. Therefore, depending on the situation, the determination of constituent monomer units is performed by comparing the spectra of both NMR and pyrolysis GC / MS. Specifically, if the resin component insoluble in deuterated chloroform, the extraction solvent used in NMR measurement, is less than 5.0% by mass, quantitative analysis is performed by NMR measurement.

[0159] On the other hand, if 5.0% or more of resin components insoluble in deuterated chloroform, the extraction solvent used during NMR measurement, are present, both NMR and thermal decomposition GC / MS measurements are performed on the deuterated chloroform-soluble components, and thermal decomposition GC / MS measurements are performed on the deuterated chloroform-insoluble components. In this case, the NMR measurement of the deuterated chloroform-soluble components is performed first to determine and quantify the constituent monomer units (quantification result 1).

[0160] Next, pyrolysis GC / MS measurement is performed on the deuterated chloroform-soluble portion, and the peak area of ​​the peaks attributed to each constituent monomer unit is determined. Using the quantitative result 1 obtained from the NMR measurement, the relationship between the amount of each constituent monomer unit and the peak area of ​​the pyrolysis GC / MS is determined. Next, pyrolysis GC / MS measurement is performed on the deuterated chloroform-insoluble portion, and the peak area of ​​the peaks attributed to each constituent monomer unit is determined. The constituent monomer units in the deuterated chloroform-insoluble portion are quantified from the relationship between the amount of each constituent monomer unit obtained from the measurement of the deuterated chloroform-soluble portion and the peak area of ​​the pyrolysis GC / MS (quantifiable result 2). Finally, quantitative result 1 and quantitative result 2 are combined to obtain the final quantitative result for each constituent monomer unit. Specifically, the following operations are performed.

[0161] (1) 500 mg of toner is accurately weighed into a 30 mL glass sample bottle, 10 mL of deuterated chloroform is added, the bottle is capped, and the toner is dispersed and dissolved using an ultrasonic disperser for 1 hour. Then, the mixture is filtered through a 0.4 μm diameter membrane filter and the filtrate is collected. At this time, the deuterated chloroform-insoluble portion remains on the membrane filter.

[0162] (2) From 3 mL of the filtrate, separate high-efficiency liquid chromatography (HPLC) is performed to remove components with a molecular weight of less than 1500 using a fraction collector, and the resin solution from which components with a molecular weight of less than 1500 have been removed is recovered. Chloroform is removed from the recovered solution using a rotary evaporator to obtain the resin. For components with a molecular weight of less than 1500, the elution time is determined in advance by measuring the molecular weight of a polystyrene resin with a known molecular weight.

[0163] (3) Dissolve 20 mg of the obtained resin in 1 mL of deuterated chloroform, 1 ¹H-NMR measurements are performed to assign spectra to each constituent monomer used in binder resins such as polyester resins and vinyl resins, and to determine quantitative values. (4) If analysis of deuterium-chloroform insoluble components is necessary, it will be performed by pyrolysis GC / MS. Derivatization treatments such as methylation will be performed as needed.

[0164] (NMR measurement conditions) Measurement device: Bruker AVANCE 500, manufactured by Bruker BioSpin Co., Ltd. Nucleus for measurement: 1 H Measurement frequency: 500.1MHz Total number of times: 16 Measurement temperature: room temperature

[0165] (Measurement conditions for pyrolysis GC / MS) Pyrolysis apparatus: TPS-700, manufactured by Nippon Analytical Industry Co., Ltd. Pyrolysis temperature: The appropriate value is between 400°C and 600°C; in this case, it is 590°C. GC / MS system: ISQ, manufactured by Thermo Fisher Scientific Co., Ltd. Column: "HP5-MS" (Agilent / 19091S-433), length 30m, inner diameter 0.25mm, film thickness 0.25μm GC / MS conditions Inlet conditions: Inlet Temp: 250℃ Split Flow: 50 ml / min GC heating conditions: 40°C (5 min) → 10°C / min (300°C) → 300°C (20 min) Mass range: m / z = 10~550

[0166] <Method for calculating the shell thickness of a core-shell structure> Cross-sectional observation of toner using a transmission electron microscope (TEM) can be performed as follows. First, toner is sprayed in a single layer onto a cover glass (Matsunami Glass Co., Ltd., Square Cover Glass No. 1), and an osmium plasma coater (filgen, OPC80T) is used to apply an Os film (5nm) and a naphthalene film (20nm) to the toner as protective films. Next, a PTFE tube (inner diameter Φ1.5mm × outer diameter Φ3mm × 3mm) is filled with photocurable resin D800 (JEOL Ltd.), and the cover glass is gently placed on top of the tube in a orientation such that the toner is in contact with the photocurable resin D800. After curing the resin by irradiating it with light in this state, the cover glass and tube are removed to form a cylindrical resin with toner embedded on the outermost surface. Using an ultrasonic ultramicrotome (Leica, UC7), the cylindrical resin is cut at a cutting speed of 0.6 mm / s to obtain a cross-section of the toner particle by cutting a length equal to the radius of the toner particle (4.0 μm if the weight-average particle size (D4) is 8.0 μm). Next, the resin is cut to a thickness of 250 nm for magnetic toner and 70 nm for non-magnetic toner to create a thin section sample of the toner particle cross-section. By cutting in this manner, a cross-section of the center of the toner particle can be obtained.

[0167] Next, the constituent elements of the cross-section of the obtained toner particles are analyzed using energy-dispersive X-ray spectroscopy (EDX), and an EDX mapping image is prepared. A transmission electron microscope (JEOL JEM-2800) (TEM-EDX) is used to magnify the image at 40,000 to 50,000 times, and the shell layer is observed from the toner cross-section, and elemental mapping is performed using EDX. In the EDX mapping image, signals originating from the constituent elements of the shell material are confirmed in the contour of the toner particle cross-section to confirm the presence or absence of the shell. The mapping conditions are a storage rate of 9,000 to 13,000 and a number of integrations of 120.

[0168] In the above EDX mapping image, the contour and center point of the toner particle cross-section are determined. The cross-section of the toner particle to be observed shall have a major axis R (μm) that satisfies the relationship 0.9 ≤ R / D4 ≤ 1.1 with respect to the weight-average particle size (D4) of the toner. The contour of the toner particle cross-section shall be along the surface of the toner particle observed in the above EDX mapping image. The center point of the toner particle cross-section shall be the geometric center of the toner particle cross-section. From the obtained center point, the toner A line is drawn along the contour of the particle cross-section. The line should form a cross with perpendicular lines at the center point of the cross-section. The shell thickness is measured at the four points at the ends of the cross lines in one toner particle cross-section. In the toner particle cross-section, the signal portion originating from the constituent elements of the shell material is defined as the shell. 100 toner cross-sections are observed, and the average shell thickness is calculated.

[0169] <Method for measuring the number-average particle size of primary silica microparticles> The number-average particle size (D1) of primary silica microparticles is calculated from images of silica microparticles on the toner surface taken with a Hitachi ultra-high-resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). The image acquisition conditions for the S-4800 are as follows.

[0170] (1) Sample preparation A thin layer of conductive paste is applied to the sample stage (aluminum sample stage, 15mm x 6mm), and toner is sprayed onto it. Excess toner is then removed from the sample stage by air blowing, and it is allowed to dry completely. The sample stage is then placed in the sample holder, and the sample stage height is adjusted to 36mm using the sample height gauge.

[0171] (2) Setting observation conditions for S-4800 The number-average particle size of primary silica nanoparticles is calculated using images obtained from backscattered electron imaging with the S-4800. Because backscattered electron images show less charge-up of silica nanoparticles compared to secondary electron images, the particle size of silica nanoparticles can be measured with high accuracy.

[0172] Fill the anti-contamination trap attached to the S-4800 housing with liquid nitrogen until it overflows, and leave it for 30 minutes. Start the S-4800's "PC-SEM" and perform flushing (cleaning of the FE tip, which is the electron source). Click on the acceleration voltage display section of the control panel on the screen, and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2 and execute. Confirm that the emission current due to flushing is 20-40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.

[0173] Click the acceleration voltage display to open the HV settings dialog, and set the acceleration voltage to [0.8kV] and the emission current to [20μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [U] and [+BSE] for the SE detector, and select [LA100] in the selection box to the right of [+BSE] to enter the mode for observing backscattered electron images. Also in the [Basic] tab of the operation panel, set the probe current to [Normal], the focus mode to [UHR], and the WD to [3.0mm] in the electron optical system conditions block. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.

[0174] (3) Calculation of the number-average particle size (D1) of silica microparticles Drag within the magnification display area of ​​the control panel to set the magnification to 100,000 (100k)x. Rotate the focus knob [COARSE] on the control panel until the image is somewhat in focus, then adjust the aperture alignment. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA / ALIGNMENT knob (X,Y) on the control panel to move the displayed beam to the center of the concentric circle. Next, select [Aperture] and rotate the STIGMA / ALIGNMENT knob (X,Y) one by one to stop or minimize the movement of the image. Close the aperture dialog and focus using autofocus. Repeat this operation two more times to focus.

[0175] Subsequently, the particle size of at least 300 silica particles on the toner surface is measured to determine the average particle size. Since some silica particles exist as aggregates, the maximum diameter of those that can be identified as primary particles is determined, and the number-average particle size of the primary silica particles is obtained by taking the arithmetic mean of the obtained maximum diameters.

[0176] <Method for measuring the weight-average particle size (D4) of toner> The weight-average particle size (D4) and number-average particle size (D1) of the toner were measured using the Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter), a precision particle size distribution analyzer using the pore electrical resistance method with a 100 μm aperture tube, and the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data. Measurements were taken with 25,000 effective measurement channels, and the measurement data was analyzed to calculate the D1 particles. The electrolytic aqueous solution used for measurement was prepared by dissolving high-grade sodium chloride in deionized water to a concentration of approximately 1% by mass; for example, "ISOTON II" (manufactured by Beckman Coulter) can be used. Prior to measurement and analysis, the dedicated software was configured as follows.

[0177] In the dedicated software's "Change Standard Measurement Method (SOM)" screen, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). Press the Threshold / Noise Level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the "Flush Aperture Tube After Measurement" option. In the dedicated software's "Pulse to Particle Size Conversion Settings" screen, set the bottle spacing to logarithmic particle size, the particle size bottle to 256 particle size bottle, and the particle size range from 2 μm to 60 μm. The specific measurement method is as follows.

[0178] 1. Pour approximately 200 ml of the electrolytic solution into a 250 ml round-bottom glass beaker specifically designed for the Multisizer 3, place it on the sample stand, and stir the mixture using the stirrer rod at 24 revolutions per second in a counterclockwise direction. Then, use the "Aperture Tube Flash" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. 2. Place approximately 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottomed glass beaker, and add approximately 0.3 ml of a diluted solution of "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted three times by mass with deionized water as a dispersant. 3. Two oscillators with an oscillation frequency of 50 kHz are built in with a phase difference of 180 degrees, and an ultrasonic dispersion device with an electrical output of 120 W, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikko Bios Co., Ltd.), into which a predetermined amount of deionized water is placed, and approximately 2 ml of the aforementioned Contaminon N is added to the water tank. 4. Place the beaker from step 2 into the beaker fixing hole of the ultrasonic disperser and activate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution inside the beaker is maximized. 5. While irradiating the electrolytic aqueous solution in the beaker described in 4. with ultrasound, add approximately 10 mg of toner to the electrolytic aqueous solution in small amounts and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank to be between 10°C and 40°C as appropriate. 6. Using a pipette, add the electrolytic aqueous solution from step 5, in which the toner is dispersed, to the round-bottom beaker from step 1, which is placed in the sample stand, and adjust the concentration to approximately 5%. Continue the measurement until the number of particles reaches 50,000. 7. The measurement data is analyzed using the dedicated software provided with the device to calculate the weight-average particle size (D4) and the number-average particle size (D1). The dedicated software also generates graphs for number %, graphs for volume %, and When these settings are configured, the "Arithmetic Diameter" values ​​in the Analysis / Number Statistics (Arithmetic Mean) and Analysis / Volume Statistics (Arithmetic Mean) screens represent the number-average particle size (D1) and weight-average particle size (D4), respectively. [Examples]

[0179] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, the parts used in the examples are measured by mass.

[0180] <Example of silica nanoparticle production> Fumed silica (silica material; spherical, BET specific surface area: 300 m²) 2 Place 100 parts of ( / g) into a reaction vessel and stir under nitrogen purge to dissolve the polydimethylsiloxane represented by formula (A) (kinematic viscosity at 25°C: 50 mm²). 2A solution prepared by diluting 20 parts of ( / s, average repeating units n=60) with 100 parts of hexane was added, and the mixture was first treated at the reaction temperature and reaction time shown in Treatment Condition 1 of Table 1 while stirring was continued. Then, a solution prepared by diluting 10 parts of polydimethylsiloxane represented by formula (B) described in Treatment Condition 2 of Table 1 with 100 parts of hexane was added, and the mixture was treated at the reaction temperature and reaction time shown in Treatment Condition 2 of Table 1. The obtained silica nanoparticles were then crushed using a pin-type crushing device to obtain silica nanoparticles 1. The number-average particle size of the primary particles of the obtained silica nanoparticles 1 was 8 nm. The physical properties of silica nanoparticles 1 are shown in Table 1.

[0181] <Manufacturing examples of silica microparticles 2-12> Silica nanoparticles 2 to 12 were produced in the same manner as the production method for silica nanoparticle 1, except that treatment conditions 1 (amount of polydimethylsiloxane added, reaction temperature, and reaction time) and treatment conditions 2 (type of polydimethylsiloxane, amount added, reaction temperature, and reaction time) were changed as shown in Table 1. The physical properties are shown in Table 1.

[0182] [Table 1]

[0183] In the table, (A) Treatment number is the number of treatments with polydimethylsiloxane represented by formula (A) per 100 parts of silica raw material (i.e., silica fine particles before surface treatment). (B) Treatment The number represents the number of polydimethylsiloxane treatments represented by formula (B) per 100 parts of silica core. The particle size indicates the number-average particle size of the primary particles.

[0184] <Example of Polyester Resin 1 Production> 100 parts of a mixture of raw material monomers other than trimellitic anhydride, mixed in the amounts shown in Table 2, and 0.52 parts of the catalyst tin di(2-ethylhexanoate) were placed in a polymerization tank equipped with a nitrogen introduction line, a dehydration line, and a stirrer. Next, the polymerization tank was subjected to a nitrogen atmosphere, and a polycondensation reaction was carried out over 6 hours while heating at 200°C. Furthermore, after raising the temperature to 210°C, trimellitic anhydride was added, and the polymerization tank was subjected to a reduced pressure of 40 kPa before the condensation reaction was carried out again. The acid value and molecular weight of the obtained resin are shown in Table 2.

[0185] <Examples of manufacturing polyester resins 2-9> In the example of producing polyester resin 1, polyester resins 2 to 9 were produced using the same procedure as for polyester resin 1, with the raw material monomer amounts shown in Table 2. During this process, sampling and measurement were performed sequentially, and the polymerization reaction was stopped when the desired molecular weight was reached, and the resin was removed from the polymerization tank. The physical properties of the obtained resins are shown in Table 2.

[0186] In polyester resins 4, 7, and 9, BPA was used as a 2-mol adduct of bisphenol A propylene oxide and a 3-mol adduct of bisphenol A ethylene oxide in a molar ratio of 80.0 to 20.0. If no specific BPA was specified, a 2-mol adduct of bisphenol A propylene oxide was used. [Table 2]

[0187] *The monomer composition is expressed as a mass percentage when the mass of the polyester composition is set to 100. The unit of acid value is mgKOH / g. The abbreviations in the table above represent, respectively: TPA: Terephthalic acid TMA: Trimellit Acid BPA: A propylene oxide or ethylene oxide adduct of bisphenol A (details as described above). EG: Ethylene glycol

[0188] <Example of Styrene Acrylic Resin 1 Production> The following materials were mixed in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, and the mixture was heated and stirred while maintaining a temperature of 180°C. • Styrene 77.0 parts n-butyl acrylate 21.0 parts • Acrylic acid 2.0 parts Xylene 300.0 parts Next, 50.0 parts of a xylene solution of 2.0% by mass of t-butyl hydroperoxide were continuously added dropwise to the system over 4.5 hours. After cooling, the solvent was separated and removed to synthesize styrene acrylic resin 1. The weight-average molecular weight Mw was 14,500 and the Tg was 65°C.

[0189] <Example of manufacturing polyester resin particle dispersion 1> Polyester resin 7 was dispersed using a disperser modified from a Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) to a high-temperature, high-pressure type. The composition ratio was 80% by mass of deionized water and 20% by mass of polyester resin. The pH was adjusted to 8.5 with ammonia, the rotor rotation speed was 60 Hz, and the pressure was 5 kg / cm². 2 The Cavitron was operated under the conditions of heating to 140°C using a heat exchanger to obtain a polyester resin particle dispersion. Ion-exchanged water was added to this dispersion to adjust the solid content to 20% by mass, and this was designated as polyester resin particle dispersion 1.

[0190] <Example of preparation of polyester resin particle dispersion 2 in the absence of organic solvents> 200 parts of polyester resin 7 and 0.2 parts of a 50% by mass aqueous solution of sodium hydroxide were fed into the raw material inlet of a twin-screw extruder (TEM-26SS, manufactured by Toshiba Machine Co., Ltd.). Additionally, 4.1 parts of a 48.5% by mass aqueous solution of sodium dodecyldiphenyl ether disulfonate (Sanyo Chemical Industries, Ltd., Eleminor MON-7) were added as a surfactant from the 4th barrel of the twin-screw extruder. The mixture was kneaded at a barrel temperature of 90°C and a screw rotation speed of 400 rpm to mix the polyester resin, sodium hydroxide, and surfactant.

[0191] 150 parts of ion-exchanged water (ion-exchanged water 1) adjusted to 90°C were added from the 5th barrel of a twin-screw extruder, 150 parts of ion-exchanged water (ion-exchanged water 2) adjusted to 90°C were added from the 7th barrel, and 150 parts of ion-exchanged water (ion-exchanged water 3) adjusted to 90°C were added from the 9th barrel, and the mixture was kneaded to obtain an aqueous dispersion of polyester resin particles. Ion-exchanged water was added to this dispersion to adjust the solid content to 20% by mass, and this was designated as polyester resin particle dispersion 2.

[0192] <Example of toner particle 1 manufacturing> Toner particles 1 were manufactured according to the following procedure. The following materials were placed in an attritor (Mitsui Miike Chemical Machinery Co., Ltd.) and dispersed using 1.7 mm diameter zirconia particles at 220 rpm for 5 hours to obtain a pigment masterbatch. • Styrene 60.0 parts • Carbon black (Orion Engineered Carbons, product name "Printex35") 7 parts • Charge control agent (Orient Co., Ltd.: Bontron E-89) 0.10 parts

[0193] 720 parts of deionized water were mixed with 450 parts of a 0.1 mol / L Na3PO4 aqueous solution and heated to 60°C. Then, 67.7 parts of a 1.0 mol / L CaCl2 aqueous solution were added to obtain an aqueous medium containing a dispersion stabilizer.

[0194] (Preparation of polymerizable monomer composition) • Styrene 14.0 parts n-butyl acrylate 26.0 parts 0.6 parts of 1,6-hexanediol diacrylate • Pigment masterbatch 67.1 units • Polyester resin 1 4.0 parts The above materials were uniformly dispersed and mixed using an attritor (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.), then heated to 60°C. 10.0 parts of paraffin wax (manufactured by Nippon Seiro Co., Ltd., HNP-51) were added and mixed as a hydrocarbon wax, and dissolved to obtain a polymerizable monomer composition.

[0195] The above polymerization monomer composition was introduced into the above aqueous medium, and stirred at 12,000 rpm for 10 minutes using a T.K. homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) under a nitrogen atmosphere at 60°C, followed by granulation. Subsequently, 8.0 parts of the polymerization initiator t-butyl peroxypivalate was added while stirring with a paddle stirring blade, and the temperature was raised to 74°C and reacted for 3 hours. After completion of the reaction, as the aforementioned high-temperature and high-pH treatment step, the suspension was heated to 100°C and held for 2 hours at a state where the pH (1) of the suspension was 5.0. Then, while the suspension was at 100°C, an aqueous solution of 0.9 mol / L-Na2CO3 was added to adjust the pH (2) of the suspension to 8.0 and held for 30 minutes. Thereafter, it was naturally cooled to room temperature to 25°C. Then, hydrochloric acid was added to the suspension and thoroughly washed to dissolve the dispersion stabilizer, followed by filtration and drying to obtain toner particles 1 with a weight average particle diameter of 7.1 μm.

[0196] <Production Examples of Toner Particles 2 to 7, and 10 and 11> For toner particles 1, except that the polyester resin type, the amount of polyester resin, and the conditions of the high-temperature and high-pH treatment step were changed as shown in Table 3, the same operations as in the production example of toner particles 1 were performed to obtain toner particles 2 to 7, 10, and 11.

[0197]

Table 3

[0198] <Production Example of Toner Particles 8> (Adjustment of Styrene-Acrylic Resin Particle Dispersion) · Styrene: 77 parts · n-Butyl Acrylate: 23 parts To the mixture and solution of the above materials, a solution prepared by dissolving 1.0 part of an anionic surfactant (Dowfax manufactured by Dow Chemical Company) in 60 parts of ion-exchanged water was added, and dispersed and emulsified in a flask to prepare an emulsion of the monomer. Subsequently, 2.0 parts of an anionic surfactant (Dowfax manufactured by Dow Chemical Company) was dissolved in 90 parts of ion-exchanged water, 2.0 parts of the emulsion of the monomer was added thereto, and further, 10 parts of ion-exchanged water in which 1.0 part of ammonium persulfate was dissolved was added. Subsequently, the remaining monomer emulsion was added over 3 hours, and the flask was purged with nitrogen. The solution in the flask was then heated in an oil bath to 65°C while stirring, and emulsion polymerization was continued for 5 hours to obtain a styrene-acrylic resin particle dispersion. The solid content of the styrene-acrylic resin particle dispersion was adjusted to 20% by mass by adding ion-exchanged water.

[0199] (Preparation of a dispersion of coloring agent particles) • Cyanide pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15:3 (copper phthalocyanine)) 45 parts • Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen®) 2 parts 250 bottles of deionized water The above ingredients were mixed and dissolved, and dispersed for about 1 hour using a high-pressure impact disperser Ultimizer (HJP30006, manufactured by Sugino Machine Co., Ltd.) to obtain a colorant particle dispersion. The volume-average particle size D50v of the particles in this colorant particle dispersion was 150 nm. Subsequently, deionized water was added to adjust the solid content concentration to 20% by mass.

[0200] (Preparation of mold release agent particle dispersion) • Paraffin-based wax (hydrocarbon wax, HNP9 manufactured by Nippon Seiro, melting point 75°C, 2nd endothermic peak temperature of wax (only one 2nd endothermic peak) 84°C): 270 parts • Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku): 13.5 parts (60% by mass of active ingredient, 3% by mass relative to the release agent) • Ion-exchanged water: 21.6 parts The above materials were mixed, and the release agent was dissolved in a pressure-discharge homogenizer (Gorin homogenizer, manufactured by Gorin Corporation) at an internal liquid temperature of 120°C. The mixture was then dispersed at a dispersion pressure of 5 MPa for 120 minutes, followed by 40 MPa for 360 minutes, and then cooled to obtain a dispersion. Deionized water was added to adjust the solid content to 20% by mass, and this was used as the release agent particle dispersion.

[0201] (Manufacturing of toner particles) • Styrene-acrylic resin particle dispersion: 375 parts • Dispersion of coloring agent particles: 75 parts • Release agent particle dispersion: 15 parts • Ion-exchanged water: 750 units • Anionic surfactant (Dowfax 2A1, manufactured by Dow Chemical): 3.2 parts The above materials were placed in a 3-liter reaction vessel equipped with a thermometer, pH meter, and stirrer as the core-forming material. After adjusting the pH to 3.0 by adding 1.0% nitric acid at a temperature of 25°C, the mixture was dispersed at 5,000 rpm using a homogenizer (IKA Ultra-Turrax T50) while 100 parts of a 2.0% by mass aqueous magnesium chloride solution were added as a flocculant and dispersed for 6 minutes.

[0202] Subsequently, the mixture was heated in a heating water bath to 53°C, with the rotation speed adjusted appropriately using an agitator to ensure the mixture was stirred. The volume-average particle size of the formed aggregated particles was measured. The particle size was checked as needed using a Ter Multisizer III, and when the volume-average particle size reached 5.0 μm, the temperature was maintained. A 1:205 part polyester resin particle dispersion was then added over 5 minutes as the material for forming the shell layer. After that, the temperature was maintained at 50°C for 30 minutes, then the temperature was raised to 90°C while adjusting the pH to 9.0, and the temperature was maintained at 90°C.

[0203] Subsequently, hydrochloric acid was added to adjust the pH(1) at 90°C to 5.0, and the mixture was stirred for another 30 minutes. Next, a 0.9 mol / L Na2CO3 aqueous solution was added to adjust the pH(2) to 5.5, and the mixture was held for 30 minutes. After that, the mixture was cooled to 25°C, filtered, and separated into solid and liquid phases, followed by washing with deionized water. After washing, the mixture was dried using a vacuum dryer to obtain toner particles 8 with a weight-average particle size of 7.2 μm.

[0204] <Example of toner particle 9 manufacturing> The following materials were thoroughly mixed in an FM mixer (manufactured by Nippon Coke Industries Co., Ltd.), and then melt-kneaded in a twin-screw kneader (manufactured by Ikegai Iron Works Co., Ltd.) set to a temperature of 100°C. • Styrene acrylic resin 1 95.0 parts • HNP9 (melting point: 76℃, manufactured by Nippon Seiro Co., Ltd.) 5.0 parts ·CIPigment Blue15:3 6.0 copies The resulting mixture was cooled and coarsely ground to a size of 1 mm or less using a hammer mill to obtain coarse material. Next, the obtained coarse material was ground to a fine particle of about 5 μm using a turbo mill manufactured by Turbo Industries Co., Ltd., and then the fine coarse powder was further cut using a multi-part classifier utilizing the Coanda effect to obtain toner base particles 1.

[0205] 720 parts of deionized water were mixed with 450 parts of a 0.1 mol / L Na3PO4 aqueous solution, heated to 60°C under an N2 atmosphere, and then 67.7 parts of a 1.0 mol / L CaCl2 aqueous solution were added to obtain an aqueous medium containing a dispersion stabilizer.

[0206] 200.0 parts of toner matrix particles 1 were added to the aforementioned aqueous medium and dispersed for 30 minutes at a temperature of 40°C using a TK homomixer while rotating at 7000 rpm. Deionized water was added to adjust the concentration of toner matrix particles in the dispersion to 20.0% by mass, thereby obtaining toner matrix particle dispersion 1.

[0207] The following samples were weighed into a reaction vessel and mixed using a propeller-type stirring blade. • Toner mother particle dispersion 1,500.0 parts • Polyester resin particle dispersion 1 20.0 parts Next, the pH of the resulting mixture was adjusted to 7.0 using a 1 mol / L NaOH aqueous solution, and the temperature of the mixture was raised to 30°C. After that, it was mixed at 200 rpm using a propeller stirring blade and held for 1.0 hour. Then, while stirring with the propeller stirring blade, the temperature was raised to 80°C at a rate of 1°C / min and held for 2 hours. After that, the resulting dispersion was stirred with a paddle stirring blade, and as part of the aforementioned high-temperature, high-pH treatment process, the suspension was heated to 90°C, hydrochloric acid was added, and the suspension was held at a pH (1) of 5.0 for 30 minutes. Then, while the suspension was still at 90°C, a 0.9 mol / L Na2CO3 aqueous solution was added to adjust the pH (2) of the suspension to 5.5 and held for 30 minutes. After that, it was allowed to cool naturally to 25°C at room temperature. After that, hydrochloric acid was added to the suspension and thoroughly washed to dissolve the dispersion stabilizer, and the mixture was filtered and dried to obtain toner particles 9 with a weight-average particle size of 7.1 μm.

[0208] <Production Example of Toner Particles 12> (Adjustment of Aqueous Medium) 14.7 parts of magnesium chloride was added to a reaction vessel containing 350.0 parts of ion-exchanged water and dissolved. Then, it was kept at 65°C for 1.0 hour while purging with nitrogen. Stirring was carried out at 12,000 rpm using a T.K. homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). While maintaining the stirring a sodium hydroxide aqueous solution in which 10.4 parts of sodium hydroxide was dissolved in 50.0 parts of ion-exchanged water was added all at once to the reaction vessel while maintaining the stirring, and an aqueous medium containing a dispersion stabilizer was prepared. Further, 1.0 mol / L hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 5.0, and an aqueous medium was prepared.

[0209] (Adjustment of Polymerizable Monomer Composition) The operation was carried out in the same manner except that polyester resin 1 of the polymerizable monomer composition of toner particles 1 was changed to polyester resin 4, and a polymerizable monomer composition was obtained.

[0210] (Granulation Step) While maintaining the temperature of the aqueous medium at 70°C and the rotation speed of the stirring device at 12,000 rpm, the polymerizable monomer composition was added to the aqueous medium, and 7.0 parts of t-butyl peroxy pivalate, which is a polymerization initiator, was added. Granulation was carried out for 10 minutes while maintaining 12,000 rpm with the stirring device as it was.

[0211] (Polymerization Step) It was changed from a high-speed stirring device to a stirrer equipped with a propeller stirring blade, and reacted at 80°C for 3 hours while stirring at 150 rpm. After the reaction was completed, as the aforementioned high-temperature and high-pH treatment step, the suspension was heated to 100°C and held for 2 hours in a state where the pH (1) of the suspension was 5.0. Then, while the suspension was at 100°C, a 0.9 mol / L - Na2CO3 aqueous solution was added to adjust the pH (2) of the suspension to 5.5 and held for 30 minutes. Then, it was naturally cooled to room temperature to 25°C. Then, hydrochloric acid was added to the suspension and washed thoroughly to dissolve the dispersion stabilizer, and filtered and dried to obtain toner particles 12 with a weight average particle diameter of 7.4 μm.

[0212] <Example of toner particle 13 manufacturing> (Addition of ammonium compounds) A 10% by mass aqueous ammonia solution was used as the ammonium compound. The ammonium compound was added to 2.5 parts per 1,000 parts of polyester resin particle dispersion and stirred for 3 minutes.

[0213] (Preparation of toner component dispersion) After adding the ammonium compound, the following components were placed in a stirring tank equipped with a thermometer, pH meter, stirrer, and jacket, and stirred for 10 minutes. The same procedure as for the colorant particle dispersion and release agent particle dispersion described in the production example of toner particles 8 was followed to obtain the colorant particle dispersion and release agent particle dispersion. • 2:635 parts of polyester resin particle dispersion with added ammonium compound • Coloring agent particle dispersion: 100 parts • Release agent particle dispersion: 20 parts • Ion-exchanged water: 200 bottles • Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 7.0 parts

[0214] While gradually adding 125 parts of an aluminum sulfate aqueous solution to the above dispersion mixture placed in a stirring tank, the mixture was introduced into a Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) through the bottom valve of the stirring tank and dispersed for 10 minutes. After the addition was complete, the jacket temperature was raised to 50°C and after 120 minutes, the particle size was measured using a Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter), and the volume-average particle size was 5.0 μm. Subsequently, 312 parts of additional polyester resin particle dispersion 1 were added and held for 30 minutes.

[0215] Subsequently, a 4% by mass sodium hydroxide aqueous solution was added to the stirred tank to adjust the pH to 9.0, and then the jacket temperature was raised to 90°C and maintained there. The samples were scanned with an optical microscope every 30 minutes. Observation of the shape and surface properties of the aggregated particles using an electron microscope (FE SEM) revealed particle coalescence after 4 hours, so the obtained slurry was cooled to 40°C. The cooled slurry was sieved using a vibrating sieve with a mesh size of 15 μm (KGC800: manufactured by Kowa Kogyosho Co., Ltd.), and then filtered using a filter press (manufactured by Tokyo Engineering Industry Co., Ltd.). Subsequently, 10 times the amount of toner particles was passed through the toner particles in the filter press to wash them. The washed toner particles were dried by cyclone collection using a loop-type airflow dryer (Flash Jet Dryer FJD-2: manufactured by Seishin Kogyo Co., Ltd.), yielding toner particles 13 with a weight-average particle diameter of 7.5 μm.

[0216] <Example of Toner 1 manufacturing> To 100 parts of toner particles, the following external additives were added and mixed in an FM mixer (manufactured by Nippon Coke Co., Ltd.) at a peripheral speed of 32 m / s for 10 minutes. Coarse particles were removed using a mesh with an opening of 45 μm to obtain toner 1. The physical properties of the obtained toner 1 are shown in Table 5. • Silica microparticles 1 1.0 part

[0217] <Manufacturing examples for toners 2-26> Except for changing the toner particles, silica microparticle types, and the number of silica microparticles added to Toner 1 as shown in Table 4, the same procedure as in the manufacturing example of Toner 1 was performed to produce Toners 2 to 26.

[0218] [Table 4]

[0219] [Table 5] Toners 1-18 and 20-26 all had one or more peaks exceeding the specified values. Toner 19 did not have any peaks exceeding the specified values.

[0220] (Examples 1-17, Comparative Examples 1-9) The following evaluations were conducted using toners 1-26 described above. The evaluation results are shown in Table 6. The evaluation methods and criteria are explained below.

[0221] A modified Canon LBP-712Ci laser printer was used as the image forming apparatus. The modification involved setting the process speed to 250 mm / sec. A commercially available Canon 040H cyan toner cartridge was used as the process cartridge. The product toner was removed from the cartridge, cleaned with compressed air, and then filled with 240 g of the toner to be evaluated. In addition, the yellow, magenta, and black stations were each fitted with yellow, magenta, and black cartridges with the toner level detection mechanism disabled, after which the evaluation was performed.

[0222] <Storage test in harsh environments> Fill the toner cartridges with 240g each of the obtained toners 1-26, and then heat them at a low temperature. The toner was left in a low-humidity environment (15°C, 10%RH) for 24 hours, then gradually changed to a high-temperature, high-humidity environment (55°C, 95%RH) over 24 hours. After being left in the high-temperature, high-humidity environment for 24 hours, it was gradually changed back to a low-temperature, low-humidity environment (15°C, 10%RH) over 24 hours. The toner was then removed after repeating the above operation for 3 cycles. The heat cycle time chart is shown in Figure 1.

[0223] To evaluate image quality after being left under the harsh conditions described above, the cartridge was left in a high-temperature, high-humidity environment (32.0°C, 80%RH) for one day, and then the image density, fogging, and vertical streaks on halftone images were evaluated in the same environment. High-temperature, high-humidity environments tend to reduce toner fluidity, making image density reduction, fogging, and vertical streaks on halftone images more likely to occur due to toner aggregation, thus requiring a stricter evaluation.

[0224] As a test of image density, one solid black image was printed with a 5mm margin at the front and 5mm margins on both sides. Image density was measured using a Macbeth densitometer (manufactured by Macbeth Corporation), a reflectance densitometer, with an SPI filter. The image density was measured at nine points in the solid black image, and the average value was evaluated as the image density. The criteria for judging image density are as follows. The evaluation results are shown in Table 6. A score of C or higher was considered good. (Evaluation criteria for image density) A: Image density is 1.40 or higher B: Image density is between 1.30 and less than 1.40 C: Image density is between 1.20 and less than 1.30 D: Image density is less than 1.20

[0225] As a test for fogging, a solid white image was printed, and its reflectance was measured using a REFLECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku Co., Ltd. The reflectance of the transfer paper (standard paper) before the solid white image was formed was also measured in the same manner. A green filter was used. The fogging was calculated from the reflectance before and after the solid white image was printed using the following formula. Reflectance (%) = Reflectance of standard paper (%) - Reflectance of white image sample (%) The criteria for judging the degree of paint overlap are as follows. The evaluation results are shown in Table 6. A score of C or higher was considered good. (Criteria for evaluating overlap) A: Fog (reflectance) is less than 1.0% B: Reflectance is between 1.0% and less than 2.0% C: Reflectance is between 2.0% and less than 3.0% D: Reflectance is 3.0% or higher

[0226] To evaluate vertical streaks on halftone images, one halftone image was printed, and the presence or absence of vertical streaks caused by toner aggregates, also known as development streaks, was visually checked. The criteria for judging vertical streaks on halftone images are as follows. The evaluation results are shown in Table 6. A rating of C or higher was considered good. (Evaluation criteria for vertical streaks in halftone images) A: No vertical lines are visible. B: Three or fewer thin lines are visible. C: Four to ten thin lines are visible. D: More than 11 stripes are visible.

[0227] <Evaluation of durability after storage testing in harsh environments> Using cartridges that have undergone the storage durability test in the harsh environment described above, a mode was set up to print two horizontal line patterns with a 4% print density per job in a high-temperature, high-humidity environment (32.0°C, 80%RH), with the machine stopping briefly between jobs before starting the next job. A total of 10,000 images were produced over four days, with 2,500 images output per day. Afterward, image density, fogging, and vertical streaks on halftone images were evaluated. The evaluation methods and criteria for image density, fogging, and halftone images were the same as those used in the storage test under harsh conditions. The evaluation results are shown in Table 6.

[0228] [Table 6]

[0229] This disclosure relates to the following configuration. (Composition 1) Toner particles containing a binder resin and hydrocarbon wax, Inorganic microparticles and A toner containing, The toner, as the inorganic fine particles, Polydimethylsiloxane represented by the following formula (A) and Polydimethylsiloxane represented by the following formula (B) It contains silica microparticles that have been surface-treated, In the analysis of organic volatile components of the silica fine particles by headspace method at a heating temperature of 150°C, the total amount of trimethylsilanol in terms of octamethyltrisiloxane, based on the mass of the silica fine particles, was 1.0 ppm or more and 5.0 ppm or less. When the toner particles are measured from the surface to a depth of 100 nm using time-of-flight secondary ion mass spectrometry, and the amount of ions in the structure shown in the following formula (C) is divided by the total amount of ions counted, the standard value is defined as follows: Within a range of 100 nm from the surface of the toner particles, there is one or more peaks of the specified value. TIFF0007837791000014.tif22170 When the maximum value among the peaks of the specified value is defined as A(dmax), and the specified value on the surface of the toner particle is defined as A(0), A(dmax) and A(0) satisfy the following equations (1) and (2) A toner characterized by the following features. 1.05≦A(dmax) / A(0)≦5.00 (1) A(0)≧0.010 ···(2) TIFF0007837791000015.tif90170 In formula (B), R 1 R is a carbinol group, hydroxyl group, epoxy group, carboxyl group, alkyl group, or hydrogen atom. 2 This is a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom. n and m are the average number of repeating units, where n is between 30 and 200, and m is between 30 and 200. Side chain in formula (B) The methyl group (-CH3) may be substituted with a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom. (Configuration 2) The toner according to configuration 1, wherein the polydimethylsiloxane represented by formula (B) is the polydimethylsiloxane represented by formula (D) below. TIFF0007837791000016.tif38170 In equation (D), p is the average number of repeating units, and is between 30 and 200. (Composition 3) The toner according to configuration 1 or 2, wherein the number-average particle size of the primary particles of the silica fine particles is 5 nm or more and 30 nm or less. (Composition 4) In the analysis by the time-of-flight secondary ion mass spectrometry method, when the standard value at a depth of 100 nm from the surface of the toner particle is defined as A(100), The above A(dmax) and A(100) satisfy the following equation (3) The toner specified in any one of items 1 to 3 of the configuration. 1.05≦A(dmax) / A(100)≦5.00 (3) (Composition 5) The aforementioned binder resin contains polyester resin, The polyester resin contains monomer units represented by the following formula (E), monomer units represented by the following formula (F), and monomer units represented by the following formula (G). The content of monomer units represented by the following formula (E) in the polyester resin is 30% by mass or more and 50% by mass or less. The content of monomer units represented by the following formula (F) in the polyester resin is 25% by mass or more and 50% by mass or less. The content of monomer units represented by the following formula (G) in the polyester resin is 0.4% by mass or more and 50% by mass or less. The toner specified in any one of items 1 to 4 of the configuration. TIFF0007837791000017.tif104170 In formula (E), R 3 R represents a benzene ring. In formula (F), R 4 R represents either an ethylene group or a propylene group, x and y are integers greater than or equal to 1, and the average value of x+y is between 2 and 10. In equation (G), R 5 This represents an ethylene group or a propylene group. (Composition 6) The aforementioned binder resin contains polyester resin, The polyester resin contains monomer units represented by the following formula (H). The toner specified in any one of items 1 to 5 of the configuration. TIFF0007837791000018.tif27170 (Composition 7) The toner according to configuration 6, wherein the content of the monomer unit represented by formula (H) in the polyester resin is 1.0% by mass or more and 4.0% by mass or less. (Composition 8) The toner particles have a core particle and a shell on the surface of the core particle, The core particles have styrene-acrylic resin, The shell has the polyester resin The toner specified in any one of items 5 to 7 of the configuration. (Composition 9) The toner according to configuration 8, wherein, in cross-sectional observation of the toner using a transmission electron microscope, the average thickness of the shell is 100 nm or more and 200 nm or less. (Composition 10) A toner containing toner particles containing styrene-acrylic resin, polyester resin, and hydrocarbon wax, and inorganic fine particles, The inorganic fine particles are polydimethylsiloxane represented by the following formula (A) and the following formula (B) It contains silica microparticles surface-treated with the indicated polydimethylsiloxane, The toner particles have a core particle and a shell on the surface of the core particle, The core particles have the styrene-acrylic resin, The shell has the polyester resin, In cross-sectional observation of the toner using a transmission electron microscope, the average thickness of the shell is between 100 nm and 200 nm. When the toner particles are measured from the surface to a depth of 100 nm using time-of-flight secondary ion mass spectrometry, and the amount of ions in the structure shown in the following formula (C) is divided by the total amount of ions counted, the standard value is defined as follows: Within a range of 100 nm from the surface of the toner particles, there is one or more peaks of the specified value. TIFF0007837791000019.tif22170 When the maximum value among the peaks of the specified value is defined as A(dmax), and the specified value on the surface of the toner particle is defined as A(0), The following equations (1) and (2) are satisfied A toner characterized by the following features. 1.05≦A(dmax) / A(0)≦5.00 (1) A(0)≧0.010 ···(2) TIFF0007837791000020.tif90170 In formula (B), R 1 R is a carbinol group, hydroxyl group, epoxy group, carboxyl group, alkyl group, or hydrogen atom. 2 is a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom. n and m are the average number of repeating units, where n is 30 or more and m is 30 or more and m is 200 or more. The methyl group (-CH3) in the side chain of formula (B) may be substituted with a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom. (Composition 11) The amount of surface treatment of the polydimethylsiloxane represented by formula (A) above is equal to the amount of silica before surface treatment. The amount is 3 to 40 parts by mass per 100 parts by mass of fine particles. In the surface treatment described above, the mass ratio (B) / (A) of the polydimethylsiloxane represented by formula (B) to the polydimethylsiloxane represented by formula (A) is 0.05 to 10.00. Toner as described in configuration 10.

Claims

1. Toner particles containing a binder resin and hydrocarbon wax, Inorganic microparticles and A toner containing, The toner, as the inorganic fine particles, Polydimethylsiloxane represented by the following formula (A) and Polydimethylsiloxane represented by the following formula (B) It contains silica microparticles that have been surface-treated, In the analysis of organic volatile components of the silica fine particles by headspace method at a heating temperature of 150°C, the total amount of trimethylsilanol in terms of octamethyltrisiloxane, based on the mass of the silica fine particles, was 1.0 ppm or more and 5.0 ppm or less. When the toner particles are measured from the surface to a depth of 100 nm using time-of-flight secondary ion mass spectrometry, and the amount of ions in the structure shown in the following formula (C) is divided by the total amount of ions counted, the standard value is defined as follows: Within a range of 100 nm from the surface of the toner particle, one or more peaks of the specified value exist. When the maximum value among the peaks of the specified value is defined as A(dmax), and the specified value on the surface of the toner particle is defined as A(0), A(dmax) and A(0) satisfy the following equations (1) and (2) A toner characterized by the following features. 1.05≦A(dmax) / A(0)≦5.00...(1) A(0)≧0.010...(2) In formula (B), R １ R is a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, an alkyl group, or a hydrogen atom. ２ is a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom. n and m are the average number of repeating units, where n is 30 or more and 200 or less, and m is 30 or more and 200 or less. The methyl group (-CH) of the side chain in formula (B) ３ These may each be substituted with a carbinol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom.

2. The toner according to claim 1, wherein the polydimethylsiloxane represented by formula (B) is the polydimethylsiloxane represented by the following formula (D). In equation (D), p is the average number of repeating units, and is between 30 and 200.

3. The toner according to claim 1 or 2, wherein the number-average particle size of the primary particles of the silica fine particles is 5 nm or more and 30 nm or less.

4. In the analysis by the time-of-flight secondary ion mass spectrometry method, when the standard value at a depth of 100 nm from the surface of the toner particle is defined as A(100), The above A(dmax) and A(100) satisfy the following formula (3) The toner according to claim 1 or 2. 1.05≦A(dmax) / A(100)≦5.00 (3)

5. The aforementioned binder resin contains polyester resin, The polyester resin contains monomer units represented by the following formula (E), monomer units represented by the following formula (F), and monomer units represented by the following formula (G). The content of the monomer unit represented by the following formula (E) in the polyester resin is 30% by mass or more and 50% by mass or less. The content of monomer units represented by the following formula (F) in the polyester resin is 25% by mass or more and 50% by mass or less. The content of monomer units represented by the following formula (G) in the polyester resin is 0.4% by mass or more and 50% by mass or less. The toner according to claim 1 or 2. In formula (E), R ３ R represents a benzene ring. In formula (F), R ４ R represents either an ethylene group or a propylene group, x and y are integers greater than or equal to 1, and the average value of x + y is between 2 and 10. In formula (G), R ５ This represents an ethylene group or a propylene group.

6. The aforementioned binder resin contains polyester resin, The polyester resin contains monomer units represented by the following formula (H). The toner according to claim 1 or 2.

7. The toner according to claim 6, wherein the content of the monomer unit represented by formula (H) in the polyester resin is 1.0% by mass or more and 4.0% by mass or less.

8. The toner particles have a core particle and a shell on the surface of the core particle, The core particles have styrene-acrylic resin, The shell has the polyester resin The toner according to claim 5.

9. The toner according to claim 8, wherein, in cross-sectional observation of the toner using a transmission electron microscope, the average value of the thickness of the shell is 100 nm or more and 200 nm or less.

10. A toner containing toner particles containing styrene-acrylic resin, polyester resin, and hydrocarbon wax, and inorganic fine particles, The inorganic fine particles contain silica fine particles surface-treated with polydimethylsiloxane represented by the following formula (A) and polydimethylsiloxane represented by the following formula (B). The toner particles have a core particle and a shell on the surface of the core particle, The core particles have the styrene-acrylic resin, The shell has the polyester resin, In cross-sectional observation of the toner using a transmission electron microscope, the average thickness of the shell is 100 nm or more and 200 nm or less. When the toner particles are measured from the surface to a depth of 100 nm using time-of-flight secondary ion mass spectrometry, and the amount of ions in the structure shown in the following formula (C) is divided by the total amount of ions counted, the standard value is defined as follows: Within a range of 100 nm from the surface of the toner particle, one or more peaks of the specified value exist. When the maximum value among the peaks of the specified value is defined as A(dmax), and the specified value on the surface of the toner particle is defined as A(0), The following equations (1) and (2) are satisfied A toner characterized by the following features. 1.05≦A(dmax) / A(0)≦5.00...(1) A(0)≧0.010...(2) In formula (B), R １ is a carbinol group, a hydroxy group, an epoxy group, a carboxy group, an alkyl group, or a hydrogen atom, and R ２ is a carbinol group, a hydroxy group, an epoxy group, a carboxy group, or a hydrogen atom. n and m are the average number of repeating units, and respectively, n is 30 or more and 200 or less, and m is 30 or more and 200 or less. The methyl group (—CH ３ ) in the side chain in formula (B) may each be substituted with a carbinol group, a hydroxy group, an epoxy group, a carboxy group, or a hydrogen atom.

11. The amount of surface treatment of the polydimethylsiloxane represented by formula (A) is 3 to 40 parts by mass per 100 parts by mass of silica fine particles before surface treatment. In the surface treatment described above, the mass ratio (B) / (A) of the polydimethylsiloxane represented by formula (B) to the polydimethylsiloxane represented by formula (A) is 0.05 to 10.

00. The toner according to claim 10.

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