toner

Abstract

To provide a toner that has a high electrification amount and high electrification maintaining properties through a series of electrophotographic processes even in a low-load process under a high temperature and high humidity, and can thereby provide an image with high definition and high reproducibility of minute dots.SOLUTION: A toner has a toner particle containing a binder resin and wax. The toner particle has a toner core particle and a protrusion present on a surface of the toner core particle. The protrusion contains an organic silicon polymer. In cross-section observation of the toner particle, when a line segment connecting both ends of an interface between the toner core particle and the protrusion is defined as a reference line, a length of the reference line as W (nm), and in a normal direction of the reference line, a maximum length of the protrusion toward a toner core particle direction with respect to the reference line as a maximum entry length I (nm), a following formula (1) is satisfied. (1) I / W≤0.050. A Young's modulus E1 of the protrusion is 1.00-3.90 GPa.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to toners for use in recording methods utilizing electrophotography, electrostatic recording, and toner jet recording. [Background technology]

[0002] Methods for visualizing image information via electrostatic latent images, such as electrophotography, are applied to copiers, multifunction machines, and printers. In recent years, as the purpose and environment of use have become more diverse, there has been a demand for even faster operation and longer life. One of the adverse effects on toners associated with the increased speed and longer life of electrophotography processes is that the toner is subjected to more stress than ever before due to friction between the various components of the image forming device. This accelerates toner deterioration, such as deformation of the toner and burial of external additives.

[0003] Conventionally, in order to control the charge characteristics of a toner, including the charge amount, a method of coating the toner surface with inorganic fine particles such as small-diameter silica has been widely used. However, it has been pointed out that these methods are prone to toner deterioration due to migration of inorganic fine particles to various components and embedding in the toner, and that there is room for improvement in charge stability throughout the life of the toner. In response to these indications, Patent Document 1 discloses a toner in which organosilicon polymer particles are fixed to the toner surface, thereby improving fluidity and improving charging properties throughout the toner's life. Patent Document 2 discloses a toner having improved charging properties by coating a core using a silane-modified resin with an organosilicon polymer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-181187 A [Patent Document 2] Patent Publication No. 2021-018335 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, in order to prevent toner deterioration, it is effective to reduce the load on the toner caused by each component. For this reason, efforts to reduce the load on the electrophotographic process have been considered. However, as the load on the electrophotographic process is reduced, the opportunity for the toner to be charged decreases, which poses an issue of reducing the charge rise speed and charge amount of the toner.

[0006] Furthermore, with the worldwide spread of electrophotography, there is a demand for toners that can secure a sufficient charge amount even in high-humidity environments that are more disadvantageous to chargeability. In high-humidity environments, it is difficult to improve the charge amount of the toner due to the influence of the moisture content in the air, and furthermore, charge retention is likely to decrease and charge distribution is likely to become broader due to charge leakage. There is also an electrophotographic process (hereinafter referred to as a two-transfer system) that has two transfer steps, namely, a primary transfer from a photoconductor to an intermediate transfer belt, and a secondary transfer from the intermediate transfer belt to paper. In particular, in such an electrophotographic process that has a long process up to printing, the charge amount of the toner is likely to decrease, which is a problem.

[0007] With toner with such a reduced charge, the force it receives from the electrostatic field during the transfer process is reduced, and the electrostatic force that propels the toner onto the paper is also reduced. As a result, the toner is prevented from propagating, and some of the toner is not transferred to the paper, resulting in missing dots, particularly in very small dots, and causing image unevenness in halftone images, which can make it difficult to obtain high-resolution images. Therefore, there is a demand for a toner that has a high charge amount even in a high-speed light-load process in a high-humidity environment and can maintain that high charge amount throughout a series of electrophotographic processes, thereby enabling reproduction of even minute dots.

[0008] Thus, in order to obtain a high-resolution image even in a light-load process in a high-humidity environment, it is important to ensure a high charge amount even in the light-load process and to maintain the desired charge amount throughout the entire electrophotographic process up to transfer onto paper. However, as a result of studies by the present inventors, it was found that the toner described in Patent Document 1 may not have a sufficient charge amount in a light load process, and there is still room for improvement in the charging characteristics.

[0009] It was also found that the toner described in Patent Document 2 did not necessarily have sufficient charge amount and charge retention in a series of electrophotographic processes in a light-load process under high temperature and high humidity conditions. As a result, in the transfer process to paper, toner with a low charge amount was generated, which sometimes prevented transfer from the intermediate transfer belt to paper as desired, and microdots could not be reproduced.

[0010] These results are believed to be due to the fact that it is difficult to ensure a high charge amount, particularly in a light load process in a high temperature and high humidity environment. In consideration of these issues, the present disclosure provides a toner that has a high charge amount and charge retention throughout a series of electrophotographic processes, even in a light-load process under high temperature and high humidity conditions, thereby enabling the production of high-resolution images with high reproducibility of microdots. [Means for solving the problem]

[0011] The present disclosure provides a toner having toner particles containing a binder resin and a wax, the toner particles have a toner core particle and a convex portion present on a surface of the toner core particle, the protrusions contain an organosilicon polymer, A line along the periphery of the surface of the toner core particle is drawn by observing the cross section of the toner particle using a transmission electron microscope, and a horizontal image is obtained by converting the line along the periphery as a reference. A line segment connecting both ends of the interface between the toner core particle and the protrusion is defined as a reference line, and the length of the reference line is defined as W (nm), In the normal direction of the reference line, the maximum length of the protrusion from the reference line to the toner core particle direction is defined as a maximum penetration length I (nm), The W and the I satisfy the following formula (1), I / W ≦ 0.050 (1) When the Young's modulus of the protrusions calculated according to Hertz's contact theory is defined as E1, the toner has E1 of 1.00 to 3.90 GPa. Effect of the Invention

[0012] According to the present disclosure, a toner can be provided that has a high charge amount and charge retention throughout a series of electrophotographic processes, even in a light-load process under high temperature and high humidity conditions, thereby enabling high-resolution images to be obtained with high reproducibility of microdots. [Brief description of the drawings]

[0013] [Figure 1] Schematic diagram of when particles have entered toner [Diagram 2] Schematic diagram of when no particles have entered the toner [Diagram 3] Schematic diagram of mixing treatment device [Figure 4] Schematic diagram of a Faraday cage DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In the present disclosure, the description of a numerical range such as "XX or more and YY or less" or "XX to YY" means a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined.

[0015] In addition, the term "monomer unit" refers to the reacted form of a monomer substance in a polymer. For example, one section of carbon-carbon bond in the main chain of a polymer in which a vinyl monomer is polymerized is considered to be one unit. The vinyl monomer can be represented by the following formula (Z). [ka]

[0016] In the formula (Z), R Z1 represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), R Z2 represents an optional substituent.

[0017] The main means for improving the amount of charge in normal frictional charging are increasing the frictional force, decreasing the humidity, increasing the contact area, and increasing the contact opportunity. For example, a method for increasing the frictional force is to increase the contact pressure between a member that carries the toner (hereinafter referred to as a carrying member) and a regulating member that regulates the toner layer thickness and is responsible for frictional charging through the regulation (hereinafter referred to as a regulating member). Another method is to increase the contact area between the carrying member and the regulating member. These methods can increase the friction, contact area, and contact opportunity between the toner and the regulating member (hereinafter referred to as toner / regulating member) and between the toner and the toner (hereinafter referred to as toner / toner), thereby increasing the charge amount of the toner. However, methods such as these that increase the contact pressure and contact area by using a member increase the load on the toner. This can accelerate toner deterioration, such as the embedding of external additives, deformation of the toner particles themselves, etc. Therefore, in order to aim for a longer-lasting electrophotographic process, a toner that can ensure a sufficient amount of charge even in a process that reduces the load caused by these components is required.

[0018] As mentioned above, when the premise is adaptation to a light load process under high humidity, a means for increasing the friction force between the toner and the regulating member to achieve the light load process cannot be adopted. In addition, the humidity cannot be controlled because it is assumed that the toner will be used in various environments, including high humidity environments. Therefore, the present inventors have considered a method for increasing the contact area between the toner and the regulating member or between the toners as a means for ensuring the amount of charge.

[0019] However, although a simple increase in the contact area can ensure the charge amount, the charge amount is likely to decrease quickly, leading to a decrease in charge retention. This is because the increase in the contact area promotes charge transfer during contact between the toner and the member or between the toner and the toner, which makes the charge more likely to leak. As a result, charge leakage occurs from the toner in the electrophotographic process downstream of the charging section, such as on the photoreceptor or the intermediate transfer belt. Due to this issue, it is difficult to achieve both a high charge amount and charge retention throughout the electrophotographic process, particularly in electrophotographic processes such as secondary transfer systems in high humidity environments.

[0020] In order to overcome this phenomenon, the present inventors have developed a method for preventing the charging of the battery in a light load process under a high humidity environment. We conducted extensive research into how to increase the contact area and how to decrease the contact area in order to maintain the charge amount in a high humidity environment. As a result of investigations by the present inventors, it has been found that by using the toner described below, it is possible to provide a toner that has excellent charging characteristics even in a light load process under high temperature and high humidity conditions and is capable of achieving high image quality.

[0021] That is, the present disclosure provides a toner having toner particles containing a binder resin and a wax, the toner particles have a toner core particle and a convex portion present on a surface of the toner core particle, the protrusions contain an organosilicon polymer, A line was drawn along the periphery of the surface of the toner core particle by observing the cross section of the toner particle using a transmission electron microscope, and a horizontal image was obtained by converting the line along the periphery as a reference. A line segment connecting both ends of the interface between the toner core particle and the protrusion is defined as a reference line, and the length of the reference line is defined as W (nm), In the normal direction of the reference line, the maximum length of the protrusion from the reference line to the toner core particle direction is defined as a maximum penetration length I (nm), The W and the I satisfy the following formula (1), I / W ≦ 0.050 (1) When the Young's modulus of the protrusions calculated according to Hertz's contact theory is defined as E1, the toner has a Young's modulus of 1.00 to 3.90 GPa.

[0022] The present inventors consider this mechanism as follows. In the above toner, assuming a negatively charged toner, the surface of the toner core particles is formed with convex portions made of an organosilicon polymer (a condensation product of an organosilicon compound) that is easily negatively charged. The convex portions have an appropriate Young's modulus E1 in a process where pressure is applied, such as during frictional charging. This appropriate Young's modulus allows the convex portions to undergo elastic deformation when subjected to pressure from a regulating member.

[0023] This allows the protrusions to be pressurized and deformed to fit the frictional charging member only during frictional charging, greatly increasing the contact area, which in turn allows charge to be efficiently transferred from the frictional charging member to the toner and between toner particles, improving the charge amount and achieving uniform charging of the toner.

[0024] On the other hand, in a non-pressurized process such as on a photoconductor or intermediate transfer belt, the convex parts do not deform, so the convex parts act as spacers between the toner and the member or between the toner and the toner, and also play a role in reducing the contact area. This makes it possible to inhibit the charge transfer between the toner and the member or between the toner and the toner, and the inventors speculate that this allows a high charge amount to be maintained.

[0025] In order to exhibit this characteristic, the Young's modulus E1 of the convex portion calculated by Hertz's contact theory must be 1.00 to 3.90 GPa. E1 is preferably 1.20 to 3.60 GPa, and more preferably 2.00 to 3.00 GPa. If E1 is less than 1.00 GPa, the projections are easily deformed, making it difficult for them to function as spacers, and the charge retention decreases.On the other hand, if E1 is more than 3.90 GPa, the projections are difficult to deform, making it difficult to increase the charge amount.

[0026] Furthermore, by observing the cross section of a toner particle using a transmission electron microscope, a line is drawn along the periphery of the surface of the toner core particle, and a horizontal image is obtained by converting the line along the periphery as a reference. In the above, a line segment connecting both ends of the interface between the toner core particle and the protrusion is defined as a reference line, and the length of the reference line is defined as W (nm). In addition, the maximum length of the protrusion in the toner core particle direction from the reference line in the normal direction to the reference line is defined as the maximum penetration length I (nm). In this case, W and I satisfy the following formula (1). I / W ≦ 0.050 (1)

[0027] Satisfying the above formula (1) indicates that the convex parts of the organosilicon polymer are in surface contact with the toner core particles. Therefore, when pressure is applied, the pressure caused by the deformation of the convex parts is evenly applied to the contact surface of the toner core particles. This promotes charge transfer from the convex parts to the toner core particles, which is thought to further improve the charge amount. As a result, dot reproducibility is also improved. If I / W is greater than the above range, the effect of improving the charge amount cannot be obtained. This is presumably because the protrusions penetrate excessively into the toner core particles, and the deformation of the protrusions is hindered by the pressure from the surrounding toner core particles. I / W must be 0.050 or less.

[0028] From the viewpoint of charge retention during durable use, I / W is preferably 0.030 or less, more preferably 0.020 or less, and even more preferably 0.010 or less. There is no particular lower limit, but it is preferably 0.000 or more, or 0.002 or more. For example, it is preferably 0.000 to 0.030, 0.000 to 0.020, 0.000 to 0.010, or 0.002 to 0.010.

[0029] One method for forming the convex portions of an organosilicon polymer is a manufacturing method called the sol-gel method. It is generally known that in a sol-gel reaction, the bonding state of the siloxane bonds formed varies depending on the acidity of the reaction medium. Specifically, when the medium is acidic, hydrogen ions electrophilically add to the oxygen of one of the reactive groups (e.g., an alkoxy group; -OR group). Next, the oxygen atom in the water molecule coordinates with the silicon atom, forming a hydrosilyl group through a substitution reaction. If there is enough water, H + Each of them attacks one oxygen atom of a reactive group (e.g., an alkoxy group; -OR group), so H in the medium + When the content of is low, the substitution reaction with hydroxyl groups is slow, and therefore the condensation polymerization reaction occurs before all of the reactive groups on the silane are hydrolyzed, making it relatively easy to produce one-dimensional linear polymers or two-dimensional polymers.

[0030] On the other hand, when the medium is alkaline, hydroxide ions are added to silicon via a pentacoordinate intermediate. This makes it easier for all reactive groups (e.g., alkoxy groups; -OR groups) to be eliminated and easily substituted with silanol groups. In particular, when a silicon compound having three or more reactive groups on the same silane is used, hydrolysis and condensation polymerization occur three-dimensionally, forming an organosilicon polymer with many three-dimensional cross-linking bonds. The reaction also finishes in a short time.

[0031] In addition, the sol-gel method starts with a solution, and forms a material by gelling the solution, so that it is possible to create various fine structures and shapes. In particular, when the toner particles are produced in an aqueous medium, the hydrophilicity of the hydrophilic groups such as the silanol groups of the organosilicon compound makes it easy to have them present on the surface of the toner core particles. Therefore, in order to form convex portions derived from an organosilicon polymer with the desired elasticity, it is preferable to carry out the sol-gel reaction in an alkaline reaction medium. When producing in an aqueous medium, it is preferable to carry out the reaction at a pH of 8.0 or higher, at a reaction temperature of 50°C or higher, and for a reaction time of 5 hours or more.

[0032] The means for adjusting the Young's modulus of the protrusions to a specific range is not particularly limited. For example, Examples of such a method include a method in which the convex portions are formed after previously treating the surfaces of the toner core particles with a small amount of an organosilicon compound depending on the type of silicon compound, and a method in which the condensation method of the organosilicon compound is adjusted by adjusting the pH, concentration, temperature, time, etc. when forming the convex portions. A more specific example is a method of utilizing the difference in the condensation reaction rate of an organosilicon compound between weakly alkaline and strongly alkaline conditions while proceeding with the sol-gel reaction in an alkaline state as described above. Here, weakly alkaline refers to a pH of about 7.8 to 9.5 (more preferably 8.0 to 8.5), and strongly alkaline refers to a pH of about 10.0 to 12.0. The inventors speculate that the reason why E1 can be controlled by these methods is because the condensation degree of the condensation product of the organosilicon compound inside or on the surface of the convex portion can be locally adjusted.

[0033] For example, the reaction may be carried out in a weakly alkaline state for about 1 to 60 minutes (preferably 5 to 20 minutes), and then adjusted to a strongly alkaline state and carried out for about 1 to 5 hours (preferably 2 to 4 hours). In this case, for example, E1 can be increased by extending the reaction time under weak alkaline conditions, and E1 can be decreased by shortening the reaction time under weak alkaline conditions.

[0034] On the other hand, I / W can be controlled by adjusting the shape of the convex portion. Specifically, I / W can be increased by increasing I or decreasing W using the method described below. Similarly, I / W can be decreased by decreasing I or increasing W. In addition, one way to increase I is to prepare a spherical organosilicon polymer in advance, and then embed it in the toner core particles by applying an external force or heat from the normal direction to create convex portions. I can be reduced by forming an organosilicon polymer in an aqueous system in which the toner core particles are dispersed and then adhering it to the surface of the toner core particles. Furthermore, W can be controlled by appropriately adjusting the pH during the reaction and the time for which said pH is maintained.

[0035] When the Young's modulus of the surface of the toner core particle is E2, the ratio of E1 to E2 (Young's modulus ratio E1 / E2) is preferably 1.0 to 4.5. When the ratio value E1 / E2 is in this range, the hardness of the protrusions relative to the surface of the toner core particle is appropriate, so that the balance between the adhesion and deformability of the protrusions to the toner core particle under the pressure process is good, and a high effect is obtained by achieving both high charging ability and charge retention. E1 / E2 is more preferably 1.5 to 4.2, and even more preferably 2.0 to 4.1. E2 can be controlled by adjusting the type and amount of the organosilicon compound moiety, such as the condensation product of an organosilicon compound, present on the outermost surface of the toner core particle. The type and amount of the condensation product of an organosilicon compound present on the outermost surface of the toner core particle can be adjusted by appropriately selecting the raw materials and the number of parts.

[0036] The toner core particles preferably have an organosilicon compound portion, and more preferably contain a condensation product of an organosilicon compound. The organosilicon compound portion is, for example, a monomer unit having an organosilicon (or a condensation product of an organosilicon compound) introduced into a binder resin. The organosilicon compound portion preferably contains at least one selected from the group consisting of an organosilicon compound and a condensation product of an organosilicon compound.

[0037] The normalized intensity (m / z=28) of the silicon ion defined as in (2) below, obtained by measuring the toner core particles with a time-of-flight secondary ion mass spectrometer (hereinafter referred to as TOF-SIMS), is taken as normalized intensity A. In this case, normalized intensity A is 8.00×10 -4 ~4.00×10 -2 It is preferable that the toner core has the normalized strength A. This means that the particle has silicon element on its surface (outermost surface). (2) Normalized intensity of silicon ion (m / z=28) = (ion intensity of silicon ion (m / z=28)) / (total ion intensity from m / z=0.5 to 1850)

[0038] This promotes charge transfer between the organosilicon polymer of the protrusions and the silicon-containing material such as the organosilicon compound moiety present on the surface of the toner core particle when the protrusions of the organosilicon polymer are elastically deformed by pressure and tightly adhere to the toner core particle. This makes it possible to further improve the charge amount. From the viewpoint of more efficient charge transfer, it is preferable that the silicon-containing material is derived from a condensation product of an organosilicon compound. From the viewpoint of charge retention, the normalized strength A is more preferably 8.00×10 -4 ~2.00×10 -2 and more preferably 8.00×10 -4 ~1.00×10 -2 and even more preferably 5.00×10 -3 ~1.00×10 -2 It is.

[0039] Furthermore, the normalized intensity of silicon ions (m / z=28) when the toner core particles are sputtered with an argon gas cluster ion beam for 250 seconds under the following condition (3) is defined as normalized intensity B. In this case, the normalized intensity B is 7.99×10 -4 It is preferable that: (3) Ar-GCIB Acceleration voltage: 5 kV, Current: 6.5 nA, Raster size: 600 μm × 600 μm, Irradiation time: 5 sec / cycle

[0040] Having the above normalized strength B under the condition (3) means that the toner core particles have silicon ions only on the surface and in the vicinity thereof. This suppresses charge leakage and improves charge retention. Also, the fixability is improved by suppressing the inhibition of thermoplasticity by silicon-containing substances. More preferably, the normalized strength B is 6.99×10 -4 The lower limit is not particularly limited, but is preferably 1.00×10 -5 That's it, 1.00 x 10-4 The above can be mentioned.

[0041] The normalized intensity A can be controlled by controlling the amount of silicon ions (m / z=28) in the vicinity of the surface of the toner core particle. The normalized intensity B can be controlled by controlling the amount of silicon ions (m / z=28) inside the toner core particles. Methods for controlling the normalized intensity of silicon ions (m / z=28) near the surface of or inside the toner core particles include, for example, methods for controlling the amount or timing of addition of an organosilicon compound for forming an organosilicon compound moiety, such as a condensation product of an organosilicon compound, or the reaction time after addition of the organosilicon compound.

[0042] The silicon element from which the normalized strength A is derived is not particularly limited, but the normalized strength A is preferably derived from a condensation product of an organosilicon compound with a silane coupling agent. The silane coupling agent is more preferably a trifunctional silane coupling agent, since it can obtain higher charging properties, and even more preferably a trifunctional silane coupling agent with a methacryloxyalkyl group as a substituent. In addition, it is preferable to add the silane coupling agent during the reaction of the toner core particles in order to cause the toner core particles to be unevenly distributed near the surface of the toner core particles.

[0043] For example, a method of adding a Si-containing monomer such as a silane coupling agent during the polymerization process of the toner core particles (for example, in the latter half of the polymerization process) to incorporate silicon into the toner core particles can be used. Another method of incorporating silicon into the toner core particles can be used by polymerizing a silane coupling agent in an aqueous medium in which the toner core particles are dispersed.

[0044] The organosilicon compound moiety contained in the toner core particle may be contained as a part of the resin, such as the binder resin, contained in the core particle. For example, the binder resin may be a compound represented by the following formula (6): The structure represented by formula (6) can be obtained by polymerizing a trifunctional silane coupling agent having a methacryloxyalkyl group with a monomer of a styrene-acrylic resin. For example, it is preferable to form toner core particles having a styrene-acrylic resin as a binder resin by a suspension polymerization method or the like, and then add a trifunctional silane coupling agent having a methacryloxyalkyl group to carry out polymerization. [ka]

[0045] (In formula (6), L 2 -COO(CH2) n - (n is an integer of 1 to 10 (preferably 2 to 8)), L 2 The carbonyl of the main chain carbon atom (R 2 R 2 represents a hydrogen atom or a methyl group.

[0046] As the silane coupling agent, known organosilicon compounds can be used without any particular limitation. Specific examples include the following bifunctional silane compounds having two functional groups and trifunctional silane compounds having three functional groups.

[0047] Examples of bifunctional silane compounds include dimethyldimethoxysilane and dimethyldiethoxysilane. Examples of trifunctional silane compounds include the following. Trifunctional silane compounds having an alkyl group as a substituent, such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, and decyltriethoxysilane; Trifunctional silane compounds having an alkenyl group as a substituent, such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane; Trifunctional silane compounds having aryl groups as substituents, such as phenyltrimethoxysilane and phenyltriethoxysilane; Trifunctional silane compounds having a methacryloxyalkyl group as a substituent, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxyoctyltrimethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, γ-methacryloxypropylethoxydimethoxysilane, and 3-methacryloxypropyltris(trimethylsiloxy)silane; Trifunctional silane compounds having an acryloxyalkyl group as a substituent, such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxyoctyltrimethoxysilane, γ-acryloxypropyldiethoxymethoxysilane, and γ-acryloxypropylethoxydimethoxysilane.

[0048] The Young's modulus E2 of the surface of the toner core particle is 0.50 GPa or more and less than 1.00 GPa. From the viewpoint of durability, E2 is preferably 0.50 GPa or more, and from the viewpoint of improving the charge amount, E2 is preferably less than 1.00 GPa. E2 is more preferably 0.60 GPa or more and 0.95 GPa or less.

[0049] The organosilicon polymer that forms the convex portions is preferably a condensation polymer of an organosilicon compound having a structure represented by the following formula (Y). [ka]

[0050] In formula (Y), Ra represents a hydrocarbon group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms), and Rb, Rc and Rd each independently represent a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group. Ra is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Rb, Rc, and Rd are each independently a halogen atom, a hydroxyl group, an acetoxy group, or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups undergo hydrolysis, addition polymerization, and condensation polymerization to form a crosslinked structure. From the viewpoint of mild hydrolysis at room temperature and deposition onto the surface of the toner core particle, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.

[0051] The hydrolysis, addition polymerization, and condensation polymerization of Rb, Rc, and Rd can be controlled by the reaction temperature, reaction time, reaction solvent, and pH. To obtain an organosilicon polymer, it is advisable to use one or more combinations of organosilicon compounds having three reactive groups (Rb, Rc, and Rd) in one molecule excluding Ra in the above formula (Y) (hereinafter also referred to as trifunctional silanes).

[0052] Examples of the compound represented by the above formula (Y) include the following. Trifunctional methylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, and methyldiethoxyhydroxysilane. Ethyltrimethoxysilane, Ethyltriethoxysilane, Ethyltrichlorosilane, Ethyltriacetoxysilane, Ethyltrihydroxysilane, Propyltrimethoxysilane, Propyltriethoxysilane, Propyltrichlorosilane, Propyltriacetoxysilane, Propyltrihydroxysilane, Butyltrimethoxysilane, Butyltriethoxysilane, Butyltrichlorosilane, Butyltriacetoxysilane, Butyltrihydroxysilane, Hexyltrimethoxysilane, Hexyltriethoxysilane, Hexyltrichlorosilane Trifunctional silanes such as hexyltriacetoxysilane, hexyltrihydroxysilane. Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0053] In addition, to the extent that the effect of the present invention is not impaired, an organosilicon polymer obtained by combining the following with an organosilicon compound having a structure represented by formula (Y) may be used. An organosilicon compound having four reactive groups in one molecule (tetrafunctional silane), an organosilicon compound having two reactive groups in one molecule (bifunctional silane), or an organosilicon compound having one reactive group (monofunctional silane). For example, the following may be mentioned. Trifunctional vinyl silanes such as dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, vinyltriisocyanatesilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, and vinyldiethoxyhydroxysilane.

[0054] It is more preferable that the organosilicon polymer of the protrusions has a structure represented by the following formula (5), since this makes it easier to obtain the desired Young's modulus E1. R-SiO 3 / 2 (5) In formula (5), R is a hydrocarbon group having 1 to 6 carbon atoms or an aryl group (preferably a phenyl group). R is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Preferred examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group, and more preferably, R is a methyl group.

[0055] Furthermore, the content of the organosilicon polymer in the toner particles is preferably from 1.0% to 10.0% by weight.

[0056] The coverage of the toner core particle surface with the convex portions containing the organosilicon polymer is preferably 30 to 70 area %, more preferably 40 to 60 area %. When the coverage is 30 area % or more, a sufficient number of convex portions can be present between the toner / regulating member and between the toner / toner to obtain the above-mentioned effect, and the charge amount is likely to be improved. When the coverage is 70 area % or less, the presence of the protrusions during fixing is unlikely to cause a filler effect, the sharp melting properties of the toner core particles are unlikely to be hindered, and gloss uniformity is likely to improve.

[0057] The surface coverage of the toner core particles can be controlled by adjusting the reactivity of the organosilicon compound during condensation. For example, the coverage can be adjusted to the above range by controlling the pH and retention time during the condensation reaction of the organosilicon compound, and the amount of the hydrolysis solution of the organosilicon compound added.

[0058] The length W of the convex portion is preferably 80 nm or more from the viewpoint of charge retention during durability, and is preferably 250 nm or less from the viewpoint of charge retention during processing. That is, W is preferably 80 to 250 nm. W is more preferably 90 to 210 nm. The maximum penetration depth I of the projections is preferably 0.3 to 2.0 nm, and more preferably It is 0.6 to 1.2 nm.

[0059] The number-average height of the convex portions measured by a scanning probe microscope is defined as H. The ratio W / H of the length W to H is preferably 1.5 to 3.7. By satisfying this W / H ratio, the balance between the contact area with the toner core particles when deformed and the contact area between the toner and the member or between the toner and the toner when not deformed is good, improving the charging characteristics. Furthermore, the migration of the convex portions is suppressed due to the improved adhesion caused by the improved contact area between the toner core particles and the convex portions, and therefore the charge retention throughout the lifespan is also improved. The W / H is more preferably from 2.0 to 3.7, and further preferably from 3.1 to 3.7. H is preferably from 25 to 100 nm, more preferably from 30 to 80 nm, and further preferably from 30 to 60 nm. H can be controlled by appropriately adjusting the number of parts of the organosilicon compound added to form the organosilicon polymer. Specifically, H can be increased by increasing the number of parts of the organosilicon compound added. H can also be decreased by decreasing the number of parts of the organosilicon compound added.

[0060] The components constituting the toner and the method for producing the toner will be described below. The toner core particles contain a binder resin, and the content of the binder resin is preferably 50% by mass or more based on the total amount of the resin components in the toner core particles. The binder resin is not particularly limited, but examples thereof include styrene-acrylic resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, mixed resins or composite resins thereof. Styrene-acrylic resin and polyester resin are preferred in terms of low cost, easy availability, and excellent low-temperature fixing. Furthermore, the binder resin more preferably contains styrene-acrylic resin in terms of excellent development durability.

[0061] Examples of the styrene-acrylic resin include polymers made of the following monofunctional polymerizable monomers or polyfunctional polymerizable monomers, copolymers obtained by combining two or more of these, and mixtures thereof.

[0062] Examples of the monofunctional polymerizable monomer include the following. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, and other styrene derivatives; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl methacrylic polymerizable monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl methacrylate; vinyl ethers such as vinyl ether, vinyl ethyl ether, and vinyl isobutyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

[0063] Examples of the polyfunctional polymerizable monomer include the following. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxy-diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol divinyl dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxy-diethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxy-polyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, etc.

[0064] The binder resin preferably contains a monomer unit derived from styrene. The content of the monomer unit derived from styrene in the binder resin is preferably 45.0 to 85.0% by mass, and more preferably 60.0 to 80.0% by mass. The binder resin preferably further contains a monomer unit of a (meth)acrylic acid alkyl ester (more preferably n-butyl acrylate) having an alkyl group having 1 to 8 carbon atoms (preferably 2 to 6 carbon atoms). The content of the monomer unit of the (meth)acrylic acid alkyl ester in the binder resin is preferably 5.0 to 40.0 mass %, more preferably 80.0 to 25.0 mass %.

[0065] Furthermore, the toner core particles contain a wax. The wax is preferably an ester wax. When the toner core particles contain an ester wax, the gloss uniformity of the image is improved even in a fixing device configuration with a low pressure.

[0066] Conventionally, high gloss has been required for high image quality in color images. In response to this requirement, it is known that the toner core particles contain an ester wax, which gives the toner core particles high sharp melting properties, and is advantageous for low temperature fixing and high gloss. However, when a shell made of an organosilicon polymer is formed on such a toner, the sharp melting property of the toner core particles is hindered to a certain extent, and sufficient low-temperature fixability and high glossiness may not be obtained. In particular, the fixing pressure is likely to be low in the center of the fixing machine due to the conventional configuration in which pressure is applied at the ends, and in such an area, the toner is not melted uniformly because less pressure is applied to the toner than at the ends of the fixing machine, and gloss may be reduced compared to the paper ends. However, when the toner has protrusions that can be deformed by pressure in the fixing nip, the deformation of the protrusions improves the adhesion and contact area between the toner particles even in areas where the fixing pressure is low. This is thought to have improved gloss uniformity by allowing heat and pressure to be applied uniformly to the toner even in a light-pressure fixing machine configuration.

[0067] The ester wax is not particularly limited, but preferably contains an ester compound of a diol and an aliphatic monocarboxylic acid. It is more preferable to contain an ester compound of an aliphatic diol and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms (preferably 14 to 18 carbon atoms). The ester wax preferably contains a monomer unit derived from ethylene glycol, that is, more preferably contains an ester compound of ethylene glycol and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms (preferably 14 to 18 carbon atoms).

[0068] Diols include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol; bisphenol A, bisphenol A derivatives such as hydrogenated bisphenol A; On the other hand, examples of the aliphatic monocarboxylic acids include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, oleic acid, vaccenic acid, linoleic acid, and linolenic acid.

[0069] The ester wax may be a single ester compound or a combination of two or more ester compounds. In addition, the above-mentioned synthetic ester wax may be used, but naturally derived ester wax such as carnauba wax or rice wax may also be used. When using a synthetic ester wax, as described above, it is preferable that at least one of the carboxylic acid component and the alcohol component does not contain a divalent or higher valent one, or contains only a small amount of the divalent one, from the viewpoint of obtaining a low molecular weight ester wax.

[0070] The molecular weight of the ester wax is preferably such that the main peak molecular weight (Mp) is in the range of 400 or more and 1,500 or less, and more preferably in the range of 500 or more and 1,000 or less.

[0071] The content of the ester wax is preferably 10.0 parts by mass or more and 25.0 parts by mass or less, and more preferably 12.0 parts by mass or more and 20.0 parts by mass or less, relative to 100 parts by mass of the binder resin. When the content of the ester wax is within the above range, it is easy to satisfy the heat resistance storage stability required for the toner.

[0072] The melting point of the ester wax is preferably from 30° C. to 120° C., and more preferably from 60° C. to 90° C. When the melting point of the ester wax is within the above range, it is easily melted in the fixing process and is less likely to impair fixability.

[0073] In addition, it is preferable that the binder resin contains a monomer unit M1 from the viewpoint of achieving higher gloss uniformity. When the SP value of the ester wax in the Fedors method is SP(W) and the SP value of the monomer unit M1 in the binder resin is SP(M1), the absolute difference between SP(M1) and SP(W), |SP(M1)-SP(W)|, is preferably 1.00 or less. The unit of the SP value is (J / cm 3 ) 0.5 It is. When the above-mentioned SP value relationship is satisfied, the compatibility between the binder resin and the ester wax can be improved, thermoplasticity can be promoted, and gloss uniformity can be further improved. From the viewpoint of storage stability, |SP(M1)-SP(W)| is more preferably 0.10 to 1.00, even more preferably 0.40 to 0.80, and even more preferably 0.50 to 0.70.

[0074] From the viewpoint of the SP value, the monomer unit M1 is more preferably a structure represented by the following formula (4). The content of the monomer unit M1 in the binder resin is preferably 3.0% by mass or more and 30.0% by mass or less, more preferably 5.0% by mass or more and 20.0% by mass or less, and even more preferably 6.0% by mass or more and 15.0% by mass or less. When the content of the normal unit M1 is within the above range, gloss uniformity can be further improved. [ka]

[0075] In the above formula (4), L 1 -COO(CH2) n -, where n is an integer of 11 to 31 (preferably 11 to 22, more preferably 11 to 18), and L 1 The carbonyl of the main chain carbon atom (R 1 R 1 represents a hydrogen atom or a methyl group.

[0076] In addition, when there are multiple types of monomer units satisfying the requirements of the monomer unit M1 in the binder resin, the value of SP(M1) is a weighted average of the SP values ​​of the respective monomer units. For example, when the monomer unit M1-1 having an SP value of SP(M1-1) is contained in an amount of A mol % based on the total number of moles of the monomer units satisfying the requirements of the monomer unit M1, and the monomer unit M1-2 having an SP value of SP(M1-2) is contained in an amount of (100-A) mol % based on the total number of moles of the monomer units satisfying the requirements of the monomer unit M1, the SP value (SP(M1)) is SP(M1) = (SP(M1-1) × A + SP(M1-2) × (100-A)) / 100. The calculation is similar when three or more types of monomer units that satisfy the requirements of the monomer unit M1 are included.

[0077] The toner particles may contain a colorant. Known pigments and dyes can be used as the colorant. Pigments are preferred as the colorant because they have excellent light resistance. Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include: CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62 and 66.

[0078] Examples of magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include: 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.

[0079] Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include: 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.

[0080] Examples of black colorants include carbon black and those toned to black using the above-mentioned yellow, magenta and cyan colorants. These colorants can be used alone or in mixture, or further in the form of a solid solution. The colorant is preferably used in an amount of 1.0 part by mass to 20.0 parts by mass relative to 100.0 parts by mass of the binder resin.

[0081] The toner can also be made magnetic by incorporating a magnetic material. In this case, the magnetic material can also serve as a colorant. Examples of magnetic materials include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

[0082] The toner particles may contain other waxes (releasing agents) in addition to the above-mentioned ester wax. Any known wax may be used without any particular limitation. Specific examples include the following. Paraffin wax, microcrystalline wax, petroleum waxes and their derivatives, such as petroleum waxes and their derivatives, montan wax and its derivatives, hydrocarbon waxes and their derivatives produced by the Fischer-Tropsch process, polyolefin waxes and their derivatives, such as polyethylene, natural waxes and their derivatives, such as carnauba wax and candelilla wax. The derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further, alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or their acid amides, esters and ketones; hydrogenated castor oil and its derivatives, vegetable waxes and animal waxes. These can be used alone or in combination.

[0083] Among these, polyolefin, Fischer-Tropsch hydrocarbon wax, and petroleum wax are preferred because they tend to improve developability and transferability. These waxes may contain an antioxidant within a range that does not affect the above effects.

[0084] The content of the other wax is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer that forms the binder resin. The melting point of the other wax is preferably from 30° C. to 120° C., more preferably from 60° C. to 100° C. By using a wax having the above-mentioned thermal properties, the releasing effect is efficiently exerted and a wider fixing area is secured.

[0085] If necessary, external additives such as various organic or inorganic fine particles may be added to the toner particles. From the viewpoint of durability when added to the toner particles, the organic or inorganic fine particles preferably have a particle size of 1 / 10 or less of the weight average particle size of the toner particles. As the organic or inorganic fine particles, for example, the following are used. (1) Fluidity imparting agents: silica, alumina, titanium oxide, carbon black and carbon fluoride. (2) Abrasives: metal oxides (e.g., strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitrides (e.g., silicon nitride), carbides (e.g., silicon carbide), metal salts (e.g., calcium sulfate, barium sulfate, calcium carbonate). (3) Lubricants: Fluorine-based resin powder (e.g., vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salts (e.g., zinc stearate, calcium stearate). (4) Charge control particles: metal oxides (e.g., tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

[0086] The organic or inorganic fine particles may be subjected to a hydrophobic treatment on the surface in order to improve the fluidity of the toner and to make the toner particles uniformly charged. Examples of the treatment agent for the hydrophobic treatment of the organic or inorganic fine powder include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds. These treatment agents may be used alone or in combination.

[0087] An example of a method for obtaining toner particles will be described below, but the method is not limited to the following. A preferred method for forming the specific convex shape on the surface of the toner core particles is to condense an organosilicon compound in an aqueous medium in which the toner core particles are dispersed, to form convex portions on the surface of the toner core particles.

[0088] When forming convex portions on the toner core particles, it is preferable to include a step (step 1) of obtaining a toner core particle dispersion in which the toner core particles are dispersed in an aqueous medium, and a step (step 2) of mixing an organosilicon compound (or a hydrolyzate thereof) with the toner core particle dispersion and causing a condensation reaction of the organosilicon compound in the toner core particle dispersion to form convex portions containing an organosilicon polymer on the toner core particles.

[0089] In step 1, the method for obtaining the toner core particle dispersion may include a method of using the dispersion of toner core particles produced in an aqueous medium as is, and a method of putting dried toner core particles into an aqueous medium and dispersing them mechanically. When dispersing dried toner core particles in an aqueous medium, a dispersion aid may be used.

[0090] As the dispersion aid, a known dispersion stabilizer or surfactant can be used. Specifically, the following can be mentioned as the dispersion stabilizer. Inorganic dispersion stabilizers such as tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina; organic dispersion stabilizers such as polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch.

[0091] Examples of the surfactant include anionic surfactants such as alkyl sulfate salts, alkylbenzene sulfonate salts, and fatty acid salts; nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxypropylene alkyl ethers; and cationic surfactants such as alkylamine salts and quaternary ammonium salts.

[0092] Among these, it is preferable to contain an inorganic dispersion stabilizer, and it is more preferable to contain a dispersion stabilizer containing a phosphate such as tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate, or aluminum phosphate.

[0093] In step 1, the toner core particle dispersion is preferably adjusted to a solids concentration of 25% by weight or more and 50% by weight or less. The pH of the toner core particle dispersion is preferably adjusted to a pH at which condensation of the organosilicon compound does not proceed easily. The pH at which condensation of the organosilicon polymer does not proceed easily varies depending on the substance, so it is preferable to adjust the pH to within ±0.5 of the pH at which the reaction does not proceed easily.

[0094] In step 2, the organosilicon compound may be added to the toner core particle dispersion liquid as it is, or may be added to the toner core particle dispersion liquid after hydrolysis. It is preferable to add the organosilicon compound after hydrolysis, since this makes it easier to control the condensation reaction and reduces the amount of the organosilicon compound remaining in the toner core particle dispersion liquid. For example, the organosilicon compound is pretreated by hydrolyzing the organosilicon compound in a separate vessel. The concentration of water from which ions have been removed, such as ion-exchanged water or RO water, is preferably 40 parts by mass to 500 parts by mass, more preferably 100 parts by mass to 400 parts by mass, based on 100 parts by mass of the organosilicon compound.

[0095] The hydrolysis is preferably carried out in an aqueous medium with pH adjusted using known acids and bases. It is known that the hydrolysis of organosilicon compounds is pH-dependent, and the pH when carrying out the hydrolysis is preferably changed appropriately depending on the type of organosilicon compound. For example, when methyltriethoxysilane is used as the organosilicon compound, the pH of the aqueous medium is preferably 2.0 or more and 6.0 or less. The hydrolysis conditions are preferably a temperature of 15 to 80°C and a time of 30 to 600 minutes.

[0096] Specific examples of acids for adjusting the pH include the following: Inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, perbromic acid, hypoiodous acid, iodous acid, iodic acid, periodic acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; organic acids such as acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, and tartaric acid. Specific examples of bases for adjusting the pH include the following: alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, etc. and their aqueous solutions; alkali metal carbonates such as potassium carbonate, sodium carbonate, lithium carbonate, etc. and their aqueous solutions; alkali metal sulfates such as potassium sulfate, sodium sulfate, lithium sulfate, etc. and their aqueous solutions; alkali metal phosphates such as potassium phosphate, sodium phosphate, lithium phosphate, etc. and their aqueous solutions; alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, etc. and their aqueous solutions; ammonia; amines such as triethylamine, etc.

[0097] In step 2, the temperature of the toner core particle dispersion is preferably adjusted to 35° C. or higher. The condensation reaction in step 2 is preferably controlled by adjusting the pH of the toner core particle dispersion. It is known that the condensation reaction of an organosilicon compound is pH-dependent, and the pH when the condensation reaction is carried out is preferably changed appropriately depending on the type of organosilicon compound. For example, when methyltrimethoxysilane is used as the organosilicon compound, the pH of the aqueous medium is preferably 6.0 or more and 12.0 or less. As the acid and base for adjusting the pH, the acid and base exemplified in the section on hydrolysis can be used. The amount of the hydrolysis liquid is adjusted to 5.0 parts by mass or more and 30.0 parts by mass or less of the organosilicon compound per 100 parts by mass of the toner core particles, which makes it easier to form convex shapes.

[0098] The characteristics of the convex portions on the surface of the toner core particles due to the condensation product of the organosilicon compound can be controlled by adjusting the reactivity of the organosilicon compound during condensation. For example, the characteristics can be adjusted to a desired range by controlling the pH, concentration, temperature, retention time, and amount of hydrolysis solution of the organosilicon compound added during the condensation reaction of the organosilicon compound. As described above, it is preferable to control the reaction using weak alkalinity and strong alkalinity.

[0099] The method for producing the toner core particles is not particularly limited, and a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, a pulverization method, etc. can be used. Among them, in the suspension polymerization method, organosilicon The polymer is easily precipitated uniformly on the surface of the toner core particles, and the organosilicon polymer has excellent adhesion, environmental stability, and an effect of suppressing the charge reversal component, as well as durability thereof. As an example, a method for obtaining toner core particles by suspension polymerization is described below.

[0100] First, a polymerizable monomer capable of forming a binder resin and, if necessary, various additives are mixed, and the materials are dissolved or dispersed using a disperser to prepare a polymerizable monomer composition. Examples of the various additives include colorants, release agents, plasticizers, charge control agents, polymerization initiators, and chain transfer agents. Examples of the dispersing machine include a homogenizer, a ball mill, a colloid mill, and an ultrasonic dispersing machine.

[0101] Next, the polymerizable monomer composition is added to an aqueous medium containing poorly water-soluble inorganic fine particles, and droplets of the polymerizable monomer composition are prepared using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser (granulation process). Thereafter, the polymerizable monomer in the droplets of the polymerizable monomer composition is polymerized to obtain toner core particles (polymerization step).

[0102] The polymerization initiator may be mixed when the polymerizable monomer composition is prepared, or may be mixed into the polymerizable monomer composition immediately before forming droplets in the aqueous medium. Alternatively, the compound may be added in a state dissolved in the polymerizable monomer or in another solvent, as required, during or after the granulation of the droplets, that is, immediately before the start of the polymerization reaction. After obtaining a binder resin by polymerizing the polymerizable monomer, a solvent removal treatment may be carried out as necessary to obtain a dispersion of toner core particles.

[0103] As the polymerization initiator, any known polymerization initiator can be used without any particular limitation. Specific examples thereof include the following. Hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert-hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, per-N-(3-tolyl)-tert-butyl palmitate-tert-butylbenzoyl peroxide Peroxide-based polymerization initiators represented by t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy pivalate, t-butyl peroxy isobutyrate, t-butyl peroxy neodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, etc.; azo- or diazo-based polymerization initiators represented by 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc.; and the like.

[0104] There is no particular limitation on the method for making the toner core particles contain the condensation product of an organosilicon compound, and a known method can be used. For example, there is a method in which a Si-containing monomer having a structure represented by (6) in a reaction form after polymerization is added during the polymerization process of the toner core particles described above to obtain a toner core particle containing the resin. Also, a method of polymerizing the monomer in an aqueous medium in which toner core particles are dispersed to obtain toner core particles containing the resin, a method of polymerizing the monomer, and using the obtained polymer as the toner core particles, A method in which the resin is added during the production process to obtain toner core particles containing the resin is exemplified.

[0105] The monomer has no particular restrictions other than having the partial structure, and specifically, the following can be mentioned. Trifunctional silane compounds having a methacryloxyalkyl group as a substituent, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxyoctyltrimethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, γ-methacryloxypropylethoxydimethoxysilane; Trifunctional silane compounds having an acryloxyalkyl group as a substituent, such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxyoctyltrimethoxysilane, γ-acryloxypropyldiethoxymethoxysilane, γ-acryloxypropylethoxydimethoxysilane, etc.

[0106] Hereinafter, various measurement methods will be described. <Measurement methods for E1 and E2> E1 and E2 are derived by performing force curve measurement on the convex portion of the organosilicon polymer on the surface of the toner particles and the surface of the toner core particles using "AFM5500M", a scanning probe microscope (SPM) manufactured by Hitachi High-Tech Corporation. The cantilever used for the measurement (hereinafter also referred to as the probe) is performed using "SI-DF3P2" sold by Hitachi High-Tech Fielding Co., Ltd. The SPM used for the measurement is calibrated in advance for the position accuracy in the XYZ directions, and the cantilever used for the measurement has the tip curvature radius of the probe measured in advance. The curvature radius of the probe tip is measured using the probe evaluation sample "TGT1-NT-MDT" sold by Hitachi High-Tech Fielding Co., Ltd. As the value of the tip curvature radius, a value that can measure the surface of the toner core particles without contacting the convex portion is selected. In the present disclosure, one with 7 nm is used.

[0107] Next, the Young's modulus is calibrated using the probe whose tip curvature radius has been confirmed. In this disclosure, calibration is performed with an accuracy of 3.0 GPa ± 5% using a PMMA (polymethyl methacrylate) plate as a standard material. After calibration, force curve measurements are performed at 100 points on the PMMA plate. In the embodiment, the average Young's modulus was 2.91 GPa. To measure toner particles, first, a conductive double-sided tape is attached to the sample stage, and toner particles are sprayed onto it. Excess toner particles are then removed from the sample stage using air blowing. The shape of this sample is measured using an AFM5500M within a 1 μm x 1 μm area on the toner particle surface, and the protrusions and the surface of the toner core particles are measured.

[0108] Whether the location where Young's modulus was measured was a convex portion containing an organosilicon polymer or the surface of a toner core particle is identified by performing SEM-EDS measurement on the toner particles where Young's modulus was measured, as described below, in a method for confirming that bright areas in a reflected electron image are derived from an organosilicon polymer. Specifically, the area where both silicon and carbon are detected in the SEM-EDS measurement is considered to be a convex portion containing an organosilicon polymer. Also, the area where silicon is not detected and carbon is detected in the SEM-EDS measurement is considered to be the surface of a toner core particle. In addition, in order to eliminate the effects of deterioration of the resin or organosilicon polymer due to electron beam irradiation during SEM-EDS measurement, SEM-EDS measurement is performed after SPM measurement to identify whether the area measured was a convex part containing the organosilicon polymer or the surface of a toner core particle.

[0109] Toner particles having a particle size equal to the weight average particle size (D4) of the toner particles are selected as the measurement object. The amount of indentation of the probe was set to one-tenth of the average height H (nm) of the convex parts. and the toner core particle surface, respectively, and the Young's modulus of each is derived based on the Hertz contact theory (select "Hertz" in the fitting model) using the load-indentation curve. In the measurement of the protrusions, the probe was pressed in to a depth that was one-tenth of the average height H (nm) of the protrusions in order to eliminate the influence of the toner core particles. For each toner particle, measurements are taken at 10 points on the protrusions and the surface of the toner core particle, and 10 toner particles are used. The average values ​​of the Young's modulus at a total of 100 points are taken as the values ​​of E1 and E2.

[0110] <Calculation of surface coverage of toner particles> (Method of Obtaining a Reflected Electron Image of the Surface of a Toner Particle) The coverage of the toner particle surface with the organosilicon polymer is calculated using a reflected electron image of the toner particle surface. A backscattered electron image of the surface of a toner particle is obtained by a scanning electron microscope (SEM). The backscattered electron images obtained from an SEM are also called "composition images," and elements with smaller atomic numbers are detected as darker, while elements with larger atomic numbers are detected as brighter. Toner particles are generally resin particles that mainly contain a carbon-based composition such as a resin component and a release agent. When an organosilicon polymer is present on the surface of a toner particle, the organosilicon polymer is observed as a bright area and the surface of the toner core particle is observed as a dark area in a backscattered electron image obtained from an SEM.

[0111] The SEM equipment and observation conditions are as follows. Equipment used: Carl Zeiss Microscopy ULTRA PLUS Acceleration voltage: 1.0 kV WD:2.0mm Aperture Size: 30.0μm Detection signal: EsB (energy selective backscattered electrons) ESB Grid: 800V Magnification: 50,000x Contrast: 63.0±5.0% (reference value) Brightness: 38.0±5.0% (reference value) Image size: 1024 x 768 pixels Pretreatment: Toner particles are scattered onto carbon tape (no deposition is performed)

[0112] Contrast and brightness are set appropriately according to the state of the device used. The accelerating voltage and EsB Grid are set to achieve the following: obtaining structural information on the outermost surface of the toner particles, preventing charge-up of undeposited samples, and selective detection of high-energy reflected electrons. The observation field is selected to be near the apex where the curvature of the toner particles is the smallest.

[0113] (Method to confirm that bright areas in a backscattered electron image are derived from organosilicon polymers) The fact that the bright areas in the observed backscattered electron image are derived from organosilicon polymers is confirmed by overlaying the backscattered electron image with an elemental mapping image obtained by energy dispersive X-ray analysis (EDS) using a scanning electron microscope (SEM). The SEM / EDS equipment and observation conditions are as follows. Equipment used (SEM): ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd. Equipment used (EDS): Thermo Fisher Scientific NORANSystem 7, Ultra Dry EDS Detector Accelerating voltage: 5.0 kV WD:7.0mm Aperture Size: 30.0μm Detection signal: SE2 (secondary electrons) Magnification: 50,000x Mode:Spectral Imaging Pretreatment: Toner particles are scattered on carbon tape and platinum sputtered. The mapping image of silicon element obtained by this method is superimposed on the above reflected electron image, and it is confirmed that the silicon atom parts of the mapping image coincide with the bright parts of the reflected electron image. The parts where both the silicon atom parts and the carbon atom parts of the mapping image coincide with the bright parts of the reflected electron image are regarded as organosilicon polymers. The organosilicon polymer and silica can be distinguished by confirming that the portion containing both silicon and carbon atoms is the organosilicon polymer.

[0114] (Method for measuring the coverage of toner particle surfaces with organosilicon polymer) The coverage is calculated based on the non-coated domain D1 that is not coated with the organosilicon polymer and the coated domain D2 that is coated with the organosilicon polymer. Domains D1 and D2 are analyzed by using the backscattered electron image of the outermost surface of the toner particles obtained by the above method, with the image processing software ImageJ (developed by Wayne Rashand). The procedure is as follows: First, convert the backscattered electron image to be analyzed to 8-bit from Type in the Image menu. Next, set the median diameter to 2.0 pixels from Filters in the Process menu to reduce image noise. After excluding the observation condition display area displayed at the bottom of the backscattered electron image, estimate the center of the image and use the Rectangle tool (Rectangle Using the tool, select a 1.5 μm square area from the center of the backscattered electron image.

[0115] Next, use the Freehand selections function in the Image menu to select only the areas where the carbon atom parts of the mapping image and the dark areas of the backscattered electron image match, and paint them all black. Also, paint everything except the areas where the carbon atom parts of the mapping image and the dark areas of the backscattered electron image match with white. Next, select Threshold from Adjust. In manual operation, select 128 as the threshold, which is the middle gradation between black and white in an 8-bit image, and click Apply to obtain a binarized image. By this operation, pixels corresponding to the non-coated domain D1 (toner core particle) are displayed in black (pixel group A1), and pixels corresponding to the coated domain D2 (organosilicon polymer) are displayed in white (pixel group A2). Again, estimate the center of the image after excluding the observation condition display area shown at the bottom of the backscattered electron image, and use the Rectangle Tool on the toolbar to select a 1.5 μm square area from the center of the backscattered electron image.

[0116] Next, use the straight line tool on the toolbar to select the scale bar in the observation condition display area shown below the backscattered electron image. In this state, select Set Scale from the Analyze menu to open a new window and enter the pixel distance of the selected straight line in the Distance in Pixels field. Enter the value of the scale bar (eg, 100) in the Known Distance field of the window, enter the unit of the scale bar (eg, nm) in the Unit of Measurement field, and click OK to complete the scale setting.

[0117] Next, select Set Measurements from the Analyze menu, check Area and Ferret's diameter, select Analyze Particles from the Analyze menu, check Display Result, and click OK to perform domain analysis. In the newly opened Results window, select the uncovered area formed by pixel group A1. The area (Area) of each domain corresponding to the covered portion domain D2 formed by the main D1 and the pixel group A2 is obtained.

[0118] The total area of ​​the uncovered domain D1 obtained is S1 (μm 2 ), and the total area of ​​the coating domain D2 is S2 (μm 2 ) The coverage rate S is calculated from the obtained S1 and S2 using the following formula. S(area%)={S2 / (S1+S2)}×100 The above procedure is carried out for 10 visual fields for the toner particles to be evaluated, and the arithmetic mean value is used as the coverage rate.

[0119] <Method for measuring the number average height H of protrusions on the surface of a toner particle> Using the AFM5500M used for measuring the Young's modulus, the convex portions on the surfaces of the toner particles are observed by the following method. The cantilever used for the measurement is SI-DF3P2, and the measurement is performed in dynamic force mode. In the same manner as the Young's modulus measurement, shape measurement is performed with AFM5500M in an area of ​​1 μm x 1 μm on the toner particle surface, and the protrusions on the toner particle surface are observed. Toner particles with a particle size equal to the weight average particle size (D4) of the toner particles are selected as the measurement subject.

[0120] After the measurement, the obtained 1 μm×1 μm measurement data is subjected to tilt correction, and then the maximum surface height Sp is calculated. The tilt correction of the measurement data is performed by performing surface correction on the measurement data in the order of linear surface correction, quadratic surface correction, and cubic surface correction. The correction is performed using the AFM5000II, which is the analysis software that comes with the AFM5500M. In the present disclosure, the tilt correction is performed on the measurement data by performing analysis processing in the order of linear surface correction (linear surface correction), quadratic surface correction (quadratic surface correction), and cubic surface correction (cubic surface correction) in the above analysis software. Sp means the maximum height from the outermost surface of the toner core particle to the apex of the protrusion in 1 μm x 1 μm. Sp can be calculated by referring to the Sp value displayed when starting the surface roughness analysis in the analysis tab of the above analysis software for the data that has been subjected to tilt correction. When the obtained Sp is the height h1 (nm) of the protrusion, the heights h1 to h50 of the protrusions of 50 toner particles are obtained by the above method, and the arithmetic mean value of h1 to h50 is taken as the average height H (nm) of the protrusions.

[0121] <Method of Obtaining Toner Particles by Removing External Additives from Toner> When analyzing and measuring the Young's modulus and other protrusions on the surface of a toner having an external additive attached to its surface, the external additive is removed by the following procedure to obtain toner particles, which are then analyzed. Add 160 g of sucrose (Kishida Chemical Co., Ltd.) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a 61.5% sucrose aqueous solution. Place 31.0 g of the above sucrose concentrated solution and 6 g of Contaminon N (product name) (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments made of nonionic surfactants, anionic surfactants, and organic builders, manufactured by Wako Pure Chemical Industries, Ltd.) in a centrifuge tube to prepare a dispersion. Add 1.0 g of toner to this dispersion and break up the toner clumps with a spatula or the like. The centrifuge tube is shaken at 300 strokes per minute (spm) for 20 minutes in a shaker (Iwaki Sangyo Co., Ltd.'s "KM Shaker" (model: V.SX)). After shaking, the solution is transferred to a glass tube for a swing rotor (50 mL) and separated in a centrifuge (H-9R, Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. Visually check that the toner particles and the aqueous solution are sufficiently separated, and collect the toner particles that have separated to the top layer with a spatula, etc. The collected toner particles are filtered through a vacuum filter and then dried in a dryer for at least one hour. The dried product is crushed with a spatula to obtain toner particles.

[0122] <Calculation method for length of convex part W and maximum penetration depth I> The cross section of the toner observed with a scanning transmission electron microscope (STEM) was prepared as follows: do. The procedure for preparing the cross section of the toner will be described below. First, the toner is spread onto a cover glass (Matsunami Glass Co., Ltd., square cover glass; square No. 1) to form a single layer, and then an osmium plasma coater (Filgen Co., Ltd., OPC80T) is used to apply an Os film (5 nm) and a naphthalene film (20 nm) to the toner as a protective film. Next, a PTFE tube (inner diameter Φ1.5 mm × outer diameter Φ3 mm × 3 mm) is filled with photocurable resin D800 (JEOL Ltd.), and the cover glass is gently placed on top of the tube so that the toner is in contact with the photocurable resin D800. In this state, the resin is hardened by irradiating it with light, and then the cover glass and tube are removed to form a cylindrical resin with the toner embedded in the outermost surface.

[0123] Using an ultrasonic ultramicrotome (Leica, UC7), a cutting speed of 0.6 mm / s is used to cut from the outermost surface of the cylindrical resin to the length of the toner radius (for example, 4.0 μm when the weight average particle size (D4) is 8.0 μm) to expose a cross section of the center of the toner. Next, a thin sample of the cross section of the toner is prepared by cutting it to a thickness of 100 nm. By cutting in this manner, a cross section of the center of the toner can be obtained. The STEM probe size is 1 nm, and the image size is 1024 x 1024 pixels. The bright field image is acquired by adjusting the Contrast on the Detector Control panel to 1425, Brightness to 3750, and the Contrast on the Image Control panel to 0.0, Brightness to 0.5, and Gamma to 1.00. The image magnification is 100,000x, and the image is acquired so that it covers about one-quarter to one-half of the circumference of the cross section of one toner particle, as shown in Figure 2.

[0124] The obtained images are analyzed using image processing software (Image J (available from https: / / imagej.nih.gov / ij / )) and the convex parts containing the organosilicon polymer are measured. Image analysis is performed on 30 STEM images. To measure, use Image J and change the scale on the image to Straight on the Straight tab. Draw a line segment equivalent to the convex width w or convex height H with Straight Line on the Straight tab, and measure it with Measure on the Analyze tab.

[0125] Figures 1 and 2 show conceptual diagrams of toner cross sections. Figure 1 is a conceptual diagram of protrusions when the maximum penetration length I is large, and Figure 2 is a conceptual diagram when the maximum penetration length I does not exist or is extremely small. First, a line is drawn along the periphery of the toner core particle surface from the toner cross-sectional image. Where the protrusions of the organosilicon polymer are embedded and penetrated into the toner core particle, a smooth line is drawn (so as to maintain the curvature of the core particle) assuming that they are not embedded. The image is then converted to a horizontal image based on the line along the periphery. In the horizontal image, in a portion where the toner core particle and the protrusion form a continuous interface, the length of the line segment (reference line) connecting both ends of the interface between the toner core particle and the protrusion is defined as W (nm) (FIGS. 1 and 2). In addition, in the normal direction of the reference line, the maximum length of the protrusion in the toner core particle direction from the reference line is defined as the maximum penetration length I (nm) (FIG. 1). In other words, when the penetration region is defined as the area closer to the center of the toner core particle than the reference line, I means the maximum depth of the penetration region in the normal direction based on the reference line. The symbols in the figure are as follows: 1: protrusion, 2: core particle surface (a line along the circumference of the core particle surface converted into a horizontal image), 3: toner core particle, 4: length W, 5: penetration depth I, 6: height H

[0126] For each of the horizontal images, the convex portions containing the organosilicon polymer were cut into long strips by the method described above. The thickness W and maximum penetration depth I are measured, and the number average of 100 values ​​is used as the values ​​of W and I. For the average height H of the convex parts, the value measured using the above-mentioned scanning probe microscope is used for more accurate measurement.

[0127] Whether or not the convex portions contain an organosilicon polymer is determined as follows. The cross section of the toner particle is observed by magnifying the thin slice sample of the toner particle with a transmission electron microscope (TEM) (JEM2800 type: manufactured by JEOL Ltd.) at a magnification of 500,000 times under conditions of an acceleration voltage of 200 V and an electron beam probe size of 1 mm. The cross section of the toner particle having a major axis of ±10% of the weight average particle diameter (D4) of the toner particle to be observed is observed. The organosilicon polymer and the toner core particles can be distinguished from each other based on the type and concentration of the constituent elements of the shell and the core. The constituent elements can be analyzed by EDS as described above. For example, since organosilicon polymers contain a large number of silicon atoms and toner core particles contain a large number of carbon atoms, organosilicon polymers can be distinguished from each other based on the ratio of silicon to carbon. Also, organosilicon polymers can be distinguished from silica by utilizing the fact that organosilicon polymers contain carbon atoms in addition to silicon atoms, while silica does not contain carbon atoms.

[0128] <Method of measuring weight average particle diameter (D4) and number average particle diameter (D1) of toner particles or toner> A precision particle size distribution measuring device using the pore electrical resistance method (product name: Coulter Counter Multisizer 3) and dedicated software (product name: Beckman Coulter Multisizer 3 Version 3.51, manufactured by Beckman Coulter, Inc.) are used. The aperture diameter is 100 μm, and measurements are performed with an effective number of measurement channels of 25,000, and the measurement data is analyzed and calculated. The electrolyte solution used for the measurement is one in which special grade sodium chloride is dissolved in ion-exchanged water to a concentration of 1 mass%, for example, ISOTON II (product name) manufactured by Beckman Coulter, Inc. can be used. Note that before performing the measurement and analysis, the dedicated software is set up as follows.

[0129] In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, set the total count number in the 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. In addition, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II (trade name), and check the aperture tube flush after measurement. In the "Pulse to particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm. The specific measurement method is as follows.

[0130] (1) Pour 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture flush" function of the analysis software to remove dirt and air bubbles from inside the aperture tube. (2) 30 mL of the aqueous electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and 0.3 mL of a diluted solution of Contaminon N (trade name) (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments, manufactured by Wako Pure Chemical Industries, Ltd.) diluted 3 times by mass with ion-exchanged water is added thereto. (3) A predetermined amount of ion-exchanged water and 2 mL of Contaminon N (trade name) are added to the water tank of an ultrasonic disperser (product name: Ultrasonic Dispersion System Tetora150, manufactured by Nikkaki Bios Co., Ltd.) that has two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees and an electrical output of 120 W. (4) The beaker (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolyte solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of toner (particles) is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to 10°C to 40°C. (6) Using a pipette, the electrolyte solution (5) in which the toner (particles) is dispersed is dropped into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to 5%. Then, the measurement is continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen is the weight average particle size (D4). When the dedicated software is set to Graph / Number %, the "Average diameter" on the "Analysis / Number Statistics (Arithmetic Mean)" screen is the number average particle size (D1).

[0131] <Wax composition analysis> The composition of the wax in the toner particles was analyzed using a nuclear magnetic resonance spectrometer ( 1 H-NMR, 13 The analysis can be performed using C-NMR and FT-IR spectroscopy. The apparatus used is described below. Each sample may be collected by separating it from the toner and analyzed. (i) 1 H-NMR, 13 C-NMR Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of times accumulated: 64 (ii) FT-IR spectrum Thermo Fisher Scientific Inc. AVATAR360FT-IR

[0132] <Method of confirming the partial structure represented by formula (5)> The structure represented by formula (5) in the organosilicon polymer contained in the toner particles can be confirmed by the following method. By using the tetrahydrofuran insoluble portion of the toner particles as a sample, the influence of the organosilicon compound portion in the toner core particles can be eliminated. The hydrocarbon group represented by R in formula (5) is 13 Confirm by C-NMR. ( 13 C-NMR (solid state) measurement conditions Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2mmφ Sample: 150 mg of tetrahydrofuran insoluble matter of toner particles for NMR measurement Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 123.25MHz ( 13 C) Reference substance: Adamantane (external standard: 29.5ppm) Sample rotation speed: 20kHz Contact time: 2ms Delay time: 2s Number of times accumulated: 1024 In this method, methyl groups (Si-CH3), ethyl groups (Si-C2H5), propyl groups (Si-C3H7), butyl groups (Si-C4H9), and pentyl groups (Si-C5H 11 ), hexyl group (Si-CH 13 The presence or absence of a signal due to a phenyl group (Si-C6H5), etc., is used to confirm the presence of the hydrocarbon group represented by R in formula (5).

[0133] In addition, solid 29 The structure bonded to Si is confirmed by Si-NMR. Specifically, the solid 29 The structure represented by formula (5) can be confirmed by confirming the T unit structure by Si-NMR. If it is necessary to confirm the structure in more detail, 1 The results of H-NMR measurements may also be used for identification.

[0134] <Separation of binder resin from toner> The various physical properties can also be measured using a binder resin separated from a toner by the following method. Weigh out 10.0 g of toner particles, place them in a cylindrical filter paper (Toyo Roshi No. 84) and place them in a Soxhlet extractor. Extract for 20 hours using 200 mL of THF as the solvent, and the solid obtained by removing the solvent from the extract is the THF-soluble portion of the toner. The THF-soluble portion contains the binder resin. Repeat this process several times to obtain the required amount of THF-soluble portion.

[0135] For the solvent gradient elution method, a gradient preparative HPLC (Shimadzu LC-20AP high pressure gradient preparative system, Waters SunFire preparative column 50mmφ250mm) is used. The column temperature is 30°C, the flow rate is 50mL / min, and the mobile phase uses acetonitrile as a poor solvent and THF as a good solvent. 0.02g of the THF soluble fraction obtained by extraction is dissolved in 1.5mL of THF to prepare the sample for separation. The mobile phase starts with a composition of 100% acetonitrile, and 5 minutes after the sample injection, the ratio of THF is increased by 4% per minute, until the mobile phase composition becomes 100% THF over 25 minutes. The components can be separated by drying the obtained fraction. Which fractional components are the binder resin will be explained later. 1 It can be distinguished by H-NMR measurement.

[0136] <Method of Identifying Monomer Units Contained in Binder Resin and Measuring the Content of Each Monomer Unit> To identify the various monomer units in the binder resin and to confirm whether the resin has the structure represented by formula (4), 1 H-NMR spectroscopy is used. The content ratio of each monomer unit in the resin is measured as follows: 1 H-NMR was performed under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of times: 64 Measurement temperature: 30℃ Sample: 50 mg of binder resin is placed in a sample tube with an inner diameter of 5 mm as a measurement sample, deuterated chloroform (CDCl3) is added as a solvent, and this is dissolved in a thermostatic bath at 40°C to prepare the sample.

[0137] Obtained 1From the H-NMR chart, a peak that is independent of the peaks that are assigned to the components of the monomer unit M1 and the components of other monomer units is selected, and the integral value i1 of this peak is calculated. Similarly, from the peaks attributable to the components of the monomer unit M2, a peak independent of the peaks attributable to the components of the monomer units derived from other monomers is selected, and the integral value i2 of this peak is calculated. Among the peaks attributable to the components of the structure (monomer unit) represented by formula (4), a peak independent of the peaks attributable to the components of the monomer unit derived from other monomers is selected, and the integral value i3 of this peak is calculated. The integral value I1 of the peak attributable to the methylene group of the polymer main chain of the resin containing the monomer unit M1 is calculated. Similarly, the integral value I2 of the peak assigned to the methylene group of the polymer main chain of the resin containing the monomer unit M2 is calculated. The integral value I3 of the peak assigned to the methylene group of the polymer main chain of the resin having the structure represented by formula (4) is calculated.

[0138] The content of the monomer unit M1 is determined using the integral values ​​i1, i2, i3 and I1, I2, I3 as follows: where n1, n2, n3, N1, N2, and N3 are the numbers of hydrogen atoms in the constituent elements to which the peak of interest for each site belongs. n1 corresponds to i1, n2 corresponds to i2, n3 corresponds to i3, N1 corresponds to I1, N2 corresponds to I2, and N3 corresponds to I3. Content of monomer unit M1 (mol%) ={(i1 / n1) / (I1 / N1)}×100 Similarly, the content of the monomer unit M2 is determined as follows. Content of monomer unit M2 (mol%) ={(i2 / n2) / (I2 / N2)}×100 Content (mol%) of the structure represented by formula (4) ={(i3 / n3) / (I3 / N3)}×100 Using the content ratio of the structure represented by formula (4) contained in the resin, calculate the content ratio of the structure represented by formula (4) based on the THF-soluble content of the toner.

[0139] <SP(M1) and SP(W) calculation method> SP(M1) and SP(W) are determined as follows according to the calculation method proposed by Fedors. For each atom or atomic group in the molecular structure, obtain the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm 3 / mol) from the table described in "Polym. Eng. Sci., 14(2), 147-154(1974)", and calculate (4.184×ΣΔei / ΣΔvi) 0.5 as the SP value (J / cm 3 ) 0.5 and so on. Specifically, obtain the evaporation energy (Δei) and molar volume (Δvi) of the monomer unit M1 and the ester wax respectively, divide the evaporation energy by the molar volume, and calculate from the following formula. SP(M1) or SP(W) = {4.184×(Σj×ΣΔei) / (Σj×ΣΔvi)} 0.5

[0140] <Measurement method of silicon ion normalized intensity (normalized intensity A) present on the surface of toner core particles> The silicon ion normalized intensity on the surface of the toner core particles is confirmed by a time-of-flight secondary ion mass spectrometer (TOF-SIMS). The used device and measurement conditions are shown below. Note that the measurement is performed on toner core particles or on toner particles from which external additives such as silica have been removed by the method described later. · Measuring device: nanoTOF II (trade name, manufactured by ULVAC-PHI, Inc.) · Primary ion species: Bi 3++ · Acceleration voltage: 30 kV · Primary ion current: 0.05 pA · Repetition frequency: 8.2 kHz Raster mode: Unbunch Raster size: 100μm×100μm Measurement mode: Positive Neutralization gun: Used Measurement time: 600 seconds Sample preparation: Toner core particles or toner particles are fixed to an indium sheet Sample pretreatment: None Using ULVAC-PHI's standard software (TOF-DR), evaluation is performed based on the mass numbers of Si ions and fragment ions originating from the resin or silane compound. The ion intensity derived from silicon with mass number 28 (m / z=28) is divided by the total ion intensity in the range of m / z=0.5 to 1850 to derive the silicon ion normalized intensity (m / z=28). The silicon ion normalized intensity (m / z=28) is derived from an organosilicon compound moiety such as a condensation product of an organosilicon compound, as described below. 29 Confirm by Si-NMR (solid state) measurement. When the toner particles contain a silicon compound other than the organosilicon compound portion, 29 The content ratio of the condensation product of the organosilicon compound to the silicon compound contained in the toner particles is derived by Si-NMR (solid state) measurement, and the value obtained by multiplying the normalized silicon ion intensity (m / z=28) by the content ratio is regarded as the intensity derived from the condensation product of the organosilicon compound.

[0141] ( 29 Si-NMR (solid state) measurement conditions Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2mmφ Sample size: 150mg Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 97.38MHz ( 29 Si) Reference material: DSS (external standard: 1.534ppm) Sample rotation speed: 10kHz Contact time: 10ms Delay time: 2s Number of times: 2000 to 8000 From the above measurements, the abundance ratio of multiple silane components according to the number of oxygen atoms bonded to Si can be determined by peak separation and integration using curve fitting.

[0142] Those having at least one of the following M unit, D unit, or T unit structures can be considered to be condensation products of organosilicon compounds. Those having the following Q unit structure can be considered to be silicon compounds other than the condensation products of organosilicon compounds. [ka]

[0143] <Removal of external additives> Add 160 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a concentrated sucrose solution. Place 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) in a centrifuge tube to prepare a dispersion. Add 1 g of toner to this dispersion and break up the toner clumps with a spatula or the like. The centrifuge tubes were shaken in a shaker (Iwaki Sangyo Co., Ltd.'s "KM Shaker") The mixture was shaken for 30 minutes at 350 reciprocations per minute. After shaking, the solution was transferred to a glass tube (50 mL) for a swing rotor and centrifuged at 58.33 S in a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.). -1 After centrifugation, the toner particles are present in the uppermost layer in the glass tube, and the external additive is present in the aqueous solution side in the lower layer. The toner particles in the top layer are collected and filtered, washed with 2 L of ion-exchanged water heated to 40° C., and the washed toner particles are taken out.

[0144] <Method for measuring normalized intensity of silicon ions (normalized intensity B) present inside toner core particles> Normally, TOF-SIMS is a surface analysis method, and the data in the depth direction is about 1 nm. Therefore, the intensity inside the toner core particle is measured after sputtering the toner core particle with an argon gas cluster ion beam (Ar-GCIB) and scraping the surface. After sputtering the toner core particles under the following condition (3), the normalized silicon ion intensity (m / z=28) measured under the same conditions as in the above “Method for measuring the normalized silicon ion intensity present on the surface of a toner core particle” is regarded as the value of the normalized silicon ion intensity present inside the toner core particle.

[0145] The sputtering conditions for Ar-GCIB (3) are as follows: Acceleration voltage: 5 kV Current: 6.5nA Raster size: 600μm×600μm Irradiation time: 5sec / cycle Sputtering time: 250 sec In addition, when we confirmed the cutting depth by sputtering a PMMA film under the same conditions in advance, we confirmed that 80 nm was removed in 250 s. EXAMPLES

[0146] The present invention will be specifically described with reference to the following Production Examples and Examples. However, these do not limit the present invention in any way. In the following formulations, "parts" and "%" are all by mass unless otherwise specified.

[0147] <Production Examples of Toner Core Particle Dispersion and Toner Core Particles> <Preparation of toner core particle dispersion 1 and production of toner core particle 1> 11.2 parts of sodium phosphate (12-hydrate) was added to a reaction vessel containing 390.0 parts of ion-exchanged water, and the mixture was kept at 65°C for 1.0 hours while purging with nitrogen. The mixture was stirred at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). While maintaining the stirring, an aqueous calcium chloride solution in which 7.4 parts of calcium chloride (2-hydrate) was dissolved in 10.0 parts of ion-exchanged water was added to the reaction vessel all at once to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 1.0 mol / L of hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0, and aqueous medium 1 was prepared.

[0148] (Preparation of Polymerizable Monomer Composition 1) Styrene 60.0 parts ·CIPigment Blue15:3 6.3 parts The above materials were placed in an attritor (manufactured by Nippon Coke & Engineering Co., Ltd.), and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5.0 hours to prepare colorant dispersion 1 in which the pigment was dispersed.

[0149] Next, the following materials were added to Colorant Dispersion 1: Styrene 16.0 parts n-Butyl acrylate 18.0 parts Lauryl acrylate 6.0 parts 1,6-Hexanediol diacrylate 0.5 parts Polyester resin 4.0 parts (Polymerization product of terephthalic acid and 2 mol propylene oxide adduct of bisphenol A, weight average molecular weight Mw=10000, acid value: 8.2 mgKOH / g) Ethylene glycol distearate 15.0 parts The above materials were kept at 65° C. and uniformly dissolved and dispersed at 500 rpm using a TK homomixer to prepare a polymerizable monomer composition 1.

[0150] (granulation process) While maintaining the temperature of the aqueous medium 1 at 70° C. and the rotation speed of the stirring device at 12,500 rpm, the polymerizable monomer composition 1 was charged into the aqueous medium 1, and 9.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. Granulation was continued for 10 minutes while maintaining the stirring device at 12,500 rpm.

[0151] (Polymerization step A) The high-speed stirrer was replaced with a stirrer equipped with a propeller stirring blade, and polymerization was carried out for 5.0 hours while stirring at 200 rpm and maintaining the temperature at 70°C.

[0152] (Polymerization step B) Continuing from the polymerization step A, the temperature was further increased to 85°C and heated for 2.0 hours to carry out a polymerization reaction. Furthermore, 0.030 parts of 3-methacryloxypropyltrimethoxysilane (S1) was added and stirred for 5 minutes, and then a 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 9.0. The temperature was further increased to 98°C and heated for 3.0 hours to remove residual monomers, and the mixture was held at 55°C for 1.0 hour while continuing to stir. Thereafter, the temperature was lowered to 25° C. Ion-exchanged water was added to adjust the toner core particle concentration in the dispersion to 20.0%, thereby obtaining toner core particle dispersion 1 in which toner core particles 1 are dispersed. On the other hand, the pH of toner core particle dispersion 1 produced in the same manner was adjusted to 1.5 with 1 mol / L hydrochloric acid, and the mixture was stirred for 1 hour, and then the mixture was washed with ion-exchanged water, filtered, and dried to obtain toner core particle 1. The physical properties of the obtained toner core particle 1 are shown in Table 1.

[0153] <Preparation of Toner Core Particle Dispersions 2 to 20, and Production Examples of Toner Core Particles 2 to 20> Toner core particle dispersions 2 to 20 and toner core particles 2 to 20 were obtained in the same manner as in the preparation of toner core particle dispersion 1 and the production of toner core particles 1, except that the parts and production conditions were changed as shown in Table 1. The physical properties of the obtained toner core particles 2 to 20 are shown in Table 1. Note that as the Si source (Si-containing monomer) in Table 1, the compounds shown in Table 2 were used.

[0154] <Preparation of toner core particle 21 and manufacturing example of toner core particle 21> <Production Example of Silane-Modified Resin 1> The following materials were charged into an autoclave equipped with a pressure reducing device, a water separating device, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and a reaction was carried out under a nitrogen atmosphere at normal pressure and 200° C. for 20 hours. Alcohol content: 80.9 parts (Bisphenol A-propylene oxide 2.0 mole adduct) Acid component 1 (terephthalic acid): 16.1 parts Acid component 2 (isophthalic acid): 16.1 parts Tetrabutoxytitanate: 0.2 parts

[0155] The following materials were then added and reacted at 220°C for 3 hours. Acid component 3 (trimellitic acid): 0.4 parts Tetrabutoxytitanate: 0.3 parts The reaction was further carried out for 2 hours under a reduced pressure of 10 to 20 mmHg. The obtained resin was dissolved in chloroform, and the solution was dropped into ethanol for reprecipitation and filtration to obtain a polyester resin.

[0156] The carboxy group in the obtained polyester resin and the amino group in the aminosilane were amidated to produce Silane-modified Resin 1 as follows. 100.0 parts of the polyester was dissolved in 400.0 parts of N,N-dimethylacetamide, and the following materials were added and stirred at room temperature for 5 hours. After the reaction was completed, the solution was dropped into methanol for reprecipitation and filtration to obtain silane-modified resin 1. Silane compound (3-aminopropyltrimethoxysilane): 0.2 parts Triethylamine: 0.3 parts Condensing agent (amidating agent): 0.3 parts [DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride]

[0157] Thereafter, using the obtained silane-modified resin 1, toner core particle dispersion 21 and toner core particles 21 were obtained in the same manner as in the preparation of toner core particle dispersion 1 and the production example of toner core particle 1, except that the following materials were added to colorant dispersion 1 in the preparation of toner core particle dispersion 1 and the production example of toner core particle 1. Styrene 20.0 parts ・20.0 parts n-butyl acrylate 1,6-Hexanediol diacrylate 0.5 parts Polyester resin 3.0 parts (Polymerization product of terephthalic acid and 2 mol propylene oxide adduct of bisphenol A, weight average molecular weight Mw=10000, acid value: 8.2 mgKOH / g) Silane modified resin 1 1.0 parts Ethylene glycol distearate 15.0 parts

[0158] [Table 1] In the table, St represents styrene and n-BA represents n-butyl acrylate. The waiting time represents the waiting time until the pH rises after the addition of the Si source. The particle size represents the weight average particle size. *1 represents the normalized intensity A of the toner core particles in a time-of-flight secondary ion mass spectrometer (TOF-SIMS). *2 represents the normalized intensity B after the toner core particles are sputtered under the above condition (3). HNP51 is paraffin wax (Nippon Seiro Co., Ltd.). Regarding normalized strength, for example, "8.36.E-03" means "8.36 x 10 -3 " indicates that.

[0159] [Table 2]

[0160] <Preparation of Monomer Hydrolyzed Solution 1> A mixture of 60 parts of ion-exchanged water adjusted to pH 4.0 with 1 mol / L hydrochloric acid and 40 parts of methyltrimethoxysilane was mixed using a stirrer until a homogeneous phase was obtained, thereby obtaining a monomer hydrolyzate solution 1.

[0161] <Preparation of Monomer Hydrolyzed Solution 2> A mixture of 60 parts of ion-exchanged water adjusted to pH 4.0 with 1 mol / L hydrochloric acid and 40 parts of methyltriethoxysilane was mixed using a stirrer until a homogeneous phase was obtained, thereby obtaining a monomer hydrolyzate liquid 2.

[0162] <Production Example of Toner Particle 1> After heating the toner core particle dispersion 1 to 55° C., the pH was adjusted to 8.0 (first pH adjustment), and 20 parts of the monomer hydrolyzate 1 was added while mixing with a propeller stirring blade, and the mixture was held for 10 minutes (first holding time). Thereafter, a 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 11.0 (second pH adjustment), and the mixture was held for 3 hours while continuing to stir. The pH was adjusted to 1.5 with 1 mol / L hydrochloric acid and stirred for 1 hour, after which the mixture was washed with ion-exchanged water, filtered and dried, and the resulting finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1.

[0163] <Production Examples of Toner Particles 2 to 23> Toner particles 2 to 23 were obtained in the same manner as in the production example of toner particle 1, except that the type of toner core particle, the monomer hydrolyzate liquid, and the production conditions were changed as shown in Table 3.

[0164] <Production Example of Comparative Toner 1> <Production Example of Organosilicon Polymer Particle 1> (first step) A reaction vessel equipped with a thermometer and a stirrer was charged with 360.0 parts of water, and 15.0 parts of hydrochloric acid with a concentration of 5.0% by mass was added to obtain a homogeneous solution. While stirring at a temperature of 25° C., 60.0 parts of methyltrimethoxysilane and 73.0 parts of tetraethoxysilane were added, and the mixture was stirred for 5 hours and then filtered to obtain a transparent reaction liquid containing a silanol compound or a partial condensate thereof.

[0165] (Second process) In a reaction vessel equipped with a thermometer, a stirrer, and a dropping device, 540.0 parts of water was placed, and 17.0 parts of ammonia water with a concentration of 10.0% by mass was added to obtain a homogeneous solution. While stirring at a temperature of 35°C, 100 parts of the reaction liquid obtained in the first step was dropped over 0.5 hours, and the mixture was stirred for 6 hours to obtain a suspension. The suspension obtained was centrifuged to precipitate and remove fine particles, and then dried for 24 hours in a dryer at a temperature of 200°C to obtain organosilicon polymer particles 1 made of polyalkylsilsesquioxane. The obtained organosilicon polymer particles 1 had a number average particle size of 95 μm as determined by scanning electron microscopy.

[0166] The following materials were then charged into a Henschel mixer ("FM-75", manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) and mixed at a rotating blade peripheral speed of 35 m / sec for a mixing time of 5 minutes, thereby adhering organosilicon polymer particles 1 to the surfaces of toner core particles 20 to obtain an externally added toner. Toner core particles classified using a multi-division classifier 20:100.0 parts Organosilicon polymer particles 1:7.0 parts

[0167] Next, the toner with the external additive was put into the inlet 45 of the mixing treatment device shown in FIG. 3 and heated. The mixing treatment device has a main casing 41 with an inner diameter of 130 mm and a treatment space 49 with a volume of 2.0×10 -3 m 3 The device was used, the rated power of the drive unit 48 was 5.5 kW, and the shapes of the rotor 42 and the stirring member 43 were as shown in FIG. 3. The overlap width d between the stirring members in FIG. 3 was set to 0.25D with respect to the maximum width D of the stirring member 43, and the clearance between the stirring member 43 and the inner circumference of the main casing 41 was set to 3.0 mm. A cooling medium was passed through the jacket 44 to adjust the temperature. Warm water was passed through the jacket so that the temperature inside the mixing treatment device became 55°C. Mixing was started after the temperature stabilized at 55°C, and adjustment was made to maintain 55°C±1°C during mixing. After the external toner is added, the power of the driving unit 48 is increased to 1.5×10 -2The toner was heated for 10 minutes while adjusting the peripheral speed of the outermost end of the stirring member 43 so as to keep the W / g (rotation speed of the drive unit 48: 150 rpm) constant. After the heating process was completed, the toner was discharged from the outlet 46 and sieved through a mesh with an opening of 75 μm to obtain a comparative toner 1.

[0168] <Production Example of Comparative Toner 2> In the manufacturing process of comparative toner 1, the silane compound added in the first step was changed to 133.0 parts of methyltrimethoxysilane to obtain organosilicon polymer particles 2. Thereafter, comparative toner 2 was obtained in the same manner as in the manufacturing example of comparative toner 1, except that the materials added were changed as follows: Toner core particles classified using a multi-division classifier 1: 100.0 parts Organosilicon polymer particles 2: 7.0 parts The resulting organosilicon polymer particles 2 had a number average particle size of 101 nm as determined by scanning electron microscope observation.

[0169] <Production Example of Comparative Toner 3> Comparative toner 3 was obtained in the same manner as in the production example of comparative toner 1, except that toner core particle 20 was changed to toner core particle 1.

[0170] <Production Example of Comparative Toner 4> (Preparation of resin particle dispersion 1) Bisphenol A propylene oxide 2 mole adduct 500 parts Terephthalic acid 154 parts Fumaric acid 45 parts Stannous octoate 2 parts The above materials were placed in a reaction vessel equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, and a polycondensation reaction was carried out at a temperature of 230°C for 8 hours. The polycondensation reaction was then continued for another hour at 8 kPa, and the mixture was then cooled to 160°C to form a polyester resin. Next, 10 parts of acrylic acid was added while keeping the temperature at 160° C., and the mixture was mixed and maintained for 15 minutes. Styrene 142 parts n-Butyl acrylate 35 parts Polymerization initiator (di-t-butyl peroxide) 10 parts After that, the mixture of the above materials was dropped using a dropping funnel over a period of 1 hour, and then the temperature was increased to 160°C. The addition polymerization reaction was carried out for 1 hour while maintaining this pressure. Thereafter, the temperature was increased to 200° C. and maintained at 10 kPa for 1 hour to obtain Polymer 1.

[0171] 100 parts of the obtained polymer 1 was dissolved in 200.0 parts of methyl ethyl ketone, and 1.0 mol / L aqueous potassium hydroxide solution was slowly added. After stirring for 10 minutes, 500.0 parts of ion-exchanged water was slowly added dropwise to emulsify. The obtained emulsion was distilled under reduced pressure to remove the solvent, and ion-exchanged water was added to adjust the resin concentration to 20%, thereby obtaining a resin particle dispersion liquid 1.

[0172] After heating the toner core particle dispersion 1 to 80°C, 1.0 mol / L potassium hydroxide aqueous solution (pH adjuster) was added while stirring to adjust the pH to 9.0, and then resin particle dispersion 1 was added while stirring at 200 rpm, and stirring was continued for 1 hour while maintaining the temperature at 80°C. After cooling to 20°C, the pH was adjusted to 1.5 with 1 mol / L hydrochloric acid and stirred for 1 hour, followed by filtration and drying while washing with ion-exchanged water, and the resulting finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect to obtain comparative toner 4. The Young's modulus, I, H, etc. in Table 3 are physical properties of resin particles.

[0173] <Production Examples of Comparative Toners 5 to 7> Comparative toners 5 to 7 were obtained in the same manner as in the production example of toner particle 1, except that the number of parts and production conditions were changed as shown in Table 3. [Table 3]

[0174] <Example 1> First, an HP Color Laser jet Enterprise M653dn was modified as an evaluation machine for an electrophotographic device, and the process speed was set to 340 mm / s, and the contact pressure of the regulating member against the toner carrier was set to 80% of the default setting. Ta. Next, a process cartridge for HP Color Laser jet Enterprise M653dn filled with toner 1 and an electrophotographic apparatus were left in a high-temperature and high-humidity environment (35° C. / 85% RH) for 48 hours in order to acclimate them to the measurement environment.

[0175] <Evaluation of initial charge> Ten solid images were printed using a modified HP Color Laser jet Enterprise M653dn machine left in the above environment. The machine was forcibly stopped during the printing of the tenth sheet, and the amount of toner charge on the support member immediately after it passed through the regulating member was measured. The amount of charge on the support member was measured using a Faraday cage shown in the perspective view of Figure 4. The inside (right side of the figure) was put into a reduced pressure state so that the toner on the support member was sucked in, and a toner filter 33 was provided to collect the toner. Reference numeral 31 denotes the suction section, and 32 denotes a holder. The charge amount per unit mass, Q / M (μC / g), was calculated from the mass M of the collected toner and the charge Q measured directly with a coulomb meter, and the toner charge amount (Q / M) was ranked as follows. In this evaluation, the higher the value, the higher the charge amount. A rating of A or B was considered to be good. The evaluation results are shown in Table 4. A: The charge on the developing roller is 50 μC / g or more. B: The charge amount on the developing roller is 40 μC / g or more and 49 μC / g or less C: The charge amount on the developing roller is 30 μC / g or more and 39 μC / g or less. D: The charge amount on the developing roller is less than 30

[0176] <Evaluation of charge retention> The modified HP Color Laser jet Enterprise M653dn machine was left in the above environment and 10 all-black images were printed, and the machine was forcibly stopped during printing to measure the toner charge amount on the intermediate transfer belt. The charge amount on the intermediate transfer belt was measured in the same manner as the evaluation of the initial charge amount. The charge amount per unit mass (μC / g) was calculated from the mass M (g) of the collected toner and the charge Q (μC) measured directly with a coulomb meter, and this was taken as the toner charge amount (Q / M). The charge retention was evaluated by comparing the charge amount on the developing roller in the above evaluation of the initial charge amount with that on the intermediate transfer belt in this evaluation.

[0177] In this evaluation, the higher the charge retention, the less likely the charge is to leak during the LBP process, and therefore the higher the charge amount is maintained. In other words, the smaller the value, the better the charge retention. Evaluations of A or B were judged to be good. The evaluation results are shown in Table 4. A: The charge difference between the developing roller and the intermediate transfer belt is 3μC / g or less B: The charge difference between the developing roller and the intermediate transfer belt is greater than 3 μC / g and less than 6 μC / g. C: The charge difference between the developing roller and the intermediate transfer belt is greater than 6 μC / g and less than 10 μC / g. D: The charge difference between the developing roller and the intermediate transfer belt is greater than 10 μC / g.

[0178] <Evaluation of Durable Charge Retention> In a high temperature and humidity environment (30°C / 80%RH), the printer was subjected to intermittent continuous use of outputting two E-letter images every four seconds with a print rate of 0.5% for 25,000 sheets. The paper used for durability evaluation was 75g / m2 2 The computer used was the Business4200 (manufactured by Xerox). After the durability test, the charge amount on the charging roller was measured in the same manner as in the evaluation of the initial charge amount. The durable charge retention was evaluated by comparing the initial charge amount with the charge amount after durability test in this evaluation. Evaluations of A to C were judged to be good. The evaluation results are shown in Table 4. A: The difference between the initial charge and the charge after durability is 3μC / g or less B: The difference between the initial charge and the charge after durability is greater than 3 μC / g and less than 6 μC / g C: The difference between the initial charge and the charge after durability is greater than 6 μC / g and less than 10 μC / g D: The difference between the initial charge and the charge after durability is 10 μC / g or more and less than 15 μC / g. E: The difference between the initial charge and the charge after durability is 15 μC / g or more.

[0179] <Light load fixing gloss uniformity evaluation> The HP Color Laser jet Enterprise M653dn was modified to have a fixing nip pressure of 80% of the default setting to be used as an electrophotographic device for evaluation, and the fixing temperature was modified to 180° C. to perform a gloss uniformity test. Under normal temperature and humidity conditions (23°C / 50% RH), the toner load on paper is 0.50 mg / cm 2 The paper was adjusted so that it was 75 g / m2, and an image was formed in landscape format with a 100% printing ratio. 2 A Business4200 (manufactured by Xerox) was used. The resulting fixed image was divided into 3 vertically and 7 horizontally (a total of 21 divisions), and the gloss was measured at each portion. The difference between the maximum and minimum values ​​(gloss difference) of the 21 measurements was calculated and evaluated according to the following evaluation criteria. The gloss measurement was performed using a PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.). Evaluations of A to C were judged to be good. The evaluation results are shown in Table 4. (Gloss uniformity evaluation criteria) A: Less than 1.0 B: 1.0 or more and less than 2.0 C: 2.0 or more and less than 3.0 D:3.0 or more

[0180] <Micro-dot reproducibility> The image quality was evaluated using the modified HP Color Laser jet Enterprise M653dn under a high temperature and humidity (H / H) environment (35°C, 85% RH). The evaluation paper had a basis weight of 75 g / m 2A business 4200 (manufactured by Xerox) was used. An image having a halftone part formed by horizontally isolated dots measuring 259 mm x 196 mm in length with a leading edge margin of 10 mm and horizontal line spacing of 10 mm was output (dot printing rate 15%). The following evaluation was performed on the 20,000th image. The evaluation was carried out by randomly observing 100 isolated dots in the image using a magnifying glass, measuring the minor and major axes of each dot, and calculating the ratio of major axis to minor axis (the value obtained by dividing the major axis by the minor axis).The maximum value of the ratio of major axis to minor axis among the 100 isolated dots was used, and a rating of A or B was determined based on the following evaluation criteria.The evaluation results are shown in Table 4. (Evaluation Criteria) A. The maximum ratio of major axis to minor axis is less than 1.10. B. The maximum ratio of major axis to minor axis is 1.10 or more and less than 1.20 C. The maximum ratio of major axis to minor axis is 1.20 or more and less than 1.30 D. The maximum ratio of major axis to minor axis is 1.30 or more.

[0181] [Table 4]

[0182] The present disclosure relates to the following configurations. (Configuration 1) A toner having toner particles containing a binder resin and a wax, The toner particles have a toner core particle and a convex portion present on a surface of the toner core particle, the protrusions contain an organosilicon polymer, A line along the periphery of the surface of the toner core particle is drawn by observing the cross section of the toner particle using a transmission electron microscope, and a horizontal image is obtained by converting the line along the periphery as a reference. A line segment connecting both ends of the interface between the toner core particle and the protrusion is defined as a reference line, and the length of the reference line is defined as W (nm), In the normal direction of the reference line, the maximum length of the protrusion from the reference line to the toner core particle direction is defined as a maximum penetration length I (nm), The W and the I satisfy the following formula (1), I / W ≦ 0.050 (1) The toner is characterized in that, when the Young's modulus of the convex portions calculated according to Hertz's contact theory is defined as E1, the E1 is 1.00 to 3.90 GPa. (Configuration 2) When the Young's modulus of the surface of the toner core particle is E2, The toner according to Configuration 1, wherein the ratio of E1 to E2 (E1 / E2) is from 1.0 to 4.5. (Configuration 3) 3. The toner according to embodiment 2, wherein E2 is 0.50 GPa or more and less than 1.00 GPa. (Configuration 4) the toner core particle contains an organosilicon compound moiety, The toner core particles are measured using a time-of-flight secondary ion mass spectrometer. The normalized intensity A is defined as the normalized intensity of silicon ions (m / z=28) defined as follows (2). The normalized intensity A is 8.00×10 -4 ~4.00×10 -2 and When the toner core particles are sputtered with an argon gas cluster ion beam for 250 seconds under the conditions of the following (3), the normalized intensity of silicon ions (m / z=28) is defined as normalized intensity B, and the normalized intensity B is 7.99×10 -4 The toner according to any one of configurations 1 to 3, which is as follows: (2) Normalized intensity of silicon ion (m / z=28) = (ion intensity of silicon ion (m / z=28)) / (total ion intensity from m / z=0.5 to 1850) (3) Acceleration voltage: 5 kV, current: 6.5 nA, raster size: 600 μm × 600 μm, exposure time: 5 sec / cycle (Configuration 5) The normalized strength A is 8.00×10 -4 ~1.00×10 -2 and The normalized intensity B is 6.99×10 -4 5. The toner according to claim 4, (Configuration 6) 6. The toner according to any one of configurations 1 to 5, wherein the coverage of the surface of the toner core particle by the convex portion is 30 to 70 area %. (Configuration 7) The organosilicon polymer has a structure represented by the following formula (5): 7. The toner according to any one of configurations 1 to 6, wherein W is 80 to 250 nm. R-SiO 3 / 2 (5) (In formula (5), R represents a hydrocarbon group having 1 to 6 carbon atoms or an aryl group.) (Configuration 8) When the number average height of the convex portions measured by a scanning probe microscope is H, The H is 25 to 100 nm, The toner according to any one of configurations 1 to 7, wherein the ratio W to H, W / H, is from 1.5 to 3.7. (Configuration 9) The wax is an ester wax, 9. The toner according to any one of configurations 1 to 8, wherein the ester wax contains an ester compound of an aliphatic diol having 2 to 6 carbon atoms and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms. (Configuration 10) The binder resin has a monomer unit M1, When the SP value of the monomer unit M1 in the Fedors method is SP(M1) and the SP value of the ester wax is SP(W), 10. The toner according to claim 9, wherein |SP(M1)-SP(W)| is 1.00 or less. (Configuration 11) The toner according to embodiment 10, wherein the monomer unit M1 has a structure represented by the following formula (4): TIFF2024011643000010.tif45153 (In the above formula (4), L 1 -COO(CH2) n - (n is an integer between 11 and 31), L 1 The carbonyl of R is attached to a carbon atom in the main chain. 1 represents a hydrogen atom or a methyl group. [Explanation of symbols]

[0183] 1: convex portion, 2: core particle surface (line along the circumference of the core particle surface converted into a horizontal image), 3: toner core particle, 4: length W, 5: penetration depth I, 6: height H

Claims

1. A toner having toner particles containing a binder resin and a wax, wherein the toner particles have toner core particles and protrusions present on the surface of the toner core particles, the protrusions contain an organosilicon polymer, by cross-sectional observation of the toner particles with a transmission electron microscope, a line is drawn along the circumference of the surface of the toner core particles, and in a horizontal image converted based on the line along the circumference, a line segment connecting both ends of the interface between the toner core particles and the protrusions is used as a reference line, and the length of the reference line is W (nm), in the normal direction of the reference line, when the maximum length of the protrusions in the direction of the toner core particles with respect to the reference line is the maximum intrusion length I (nm), the W and the I satisfy the following formula (1), I / W ≦ 0.050... (1) When the Young's modulus of the protrusions calculated by Hertz's contact theory is E1, the toner is characterized in that the E1 is 1.00 to 3.90 GPa.

2. When the Young's modulus of the surface of the toner core particles is E2, the toner according to claim 1, wherein the value of the ratio (E1 / E2) of the E1 to the E2 is 1.0 to 4.

5.

3. The toner according to claim 2, wherein the E2 is 0.50 GPa or more and less than 1.00 GPa.

4. The toner core particles contain an organosilicon compound moiety, When the normalized intensity (m / z = 28) of silicon ions defined as in the following (2), which is obtained by measuring the toner core particles with a time-of-flight secondary ion mass spectrometer, is taken as the normalized intensity A, the normalized intensity A is 8.00×10 －４ ~4.00×10 －２ and When the normalized intensity of silicon ions (m / z = 28) when sputtering the toner core particles with an argon gas cluster ion beam for 250 seconds under the following condition (3) is defined as the normalized intensity B, the normalized intensity B is 7.99×10 －４ The toner according to any one of claims 1 to 3, which is as follows. (2) Normalized intensity of silicon ions (m / z = 28) = (Ion intensity of silicon ions (m / z = 28)) / (Total ion intensity at m / z = 0.5 to 1850) (3) Acceleration voltage: 5 kV, current: 6.5 nA, raster size: 600 μm × 600 μm, irradiation time: 5 sec / cycle

5. The normalized intensity A is 8.00×10 －４ to 1.00×10 －２ and The normalized strength B is 6.99×10 －４ The toner according to claim 4, wherein the value is 6.99×10

6. The toner according to any one of claims 1 to 3, wherein the coverage rate of the surface of the toner core particles by the protrusions is 30 to 70 area%.

7. The organosilicon polymer has a structure represented by the following formula (5), The toner according to any one of claims 1 to 3, wherein the W is 80 to 250 nm. R—SiO ３／２ ・・・(5) (In formula (5), R represents a hydrocarbon group or an aryl group having 1 to 6 carbon atoms.)

8. When the number average height of the protrusions measured by a scanning probe microscope is H, the H is 25 to 100 nm, The toner according to any one of claims 1 to 3, wherein the value of the ratio W / H of the W to the H is 1.5 to 3.

7.

9. The wax is an ester wax, The toner according to any one of claims 1 to 3, wherein the ester wax contains an ester compound of an aliphatic diol having 2 to 6 carbon atoms and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms.

10. The binder resin has a monomer unit M1, When the SP value of the monomer unit M1 in the fedors method is defined as SP(M1) and the SP value of the ester wax is defined as SP(W), The toner according to claim 9, wherein │SP(M1) - SP(W)│ is 1.00 or less.

11. The toner according to claim 10, wherein the monomer unit M1 has a structure represented by the following formula (4). (In the above formula (4), L １ represents -COO(CH ２ ), ｎ where n is an integer from 11 to 31, and the carbonyl of L １ is bonded to the carbon atom of the main chain. R １ represents a hydrogen atom or a methyl group.)

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