Toner, external additive for toner, and fine particles

Abstract

The present invention relates to toner, toner external additive, and fine particles. A toner comprising: toner particles including a binder resin and a colorant; and fine particles on a surface of the toner particles, wherein the fine particles are solid and substantially hemispherical, and have a substantially flat surface and a curved surface, and wherein a number average of a longest diameter "w" of the substantially flat surface is 10 to 400 nm. A toner external additive which is solid and substantially hemispherical, and has a substantially flat surface and a curved surface, wherein a number average of a longest diameter "w" of the substantially flat surface is 10 to 400 nm. A fine particle which is solid and substantially hemispherical, and has a substantially flat surface and a curved surface, wherein a number average of a longest diameter "w" of the substantially flat surface is 10 to 400 nm.

Description

Technical Field

[0001] This invention relates to toners, external additives for toners, and fine particles for developing electrostatic images used in image forming methods such as electrophotography and electrostatic printing. Background Technology

[0002] Typical devices employing toners in electrophotographic systems include, for example, laser printers or copiers. In recent years, there has been a growing demand for reduced power consumption, miniaturization, and improved image quality in such devices; therefore, various studies have been conducted to develop superior toners that meet these requirements.

[0003] In these studies, methods including adding various fine particles to the surface of toner particles in toner are well known. Japanese Patent Application Publication No. 2017-138482 proposes a toner with excellent transfer and cleaning properties obtained by adding fine particles of specific size, aspect ratio, and shape to the surface of toner particles with high roundness. However, with continuous use of the toner, the migration of external additives from the surface of the toner particles to any other component, as well as the rolling and embedding of external additives on the surface of the toner particles, remain problems. In particular, in recent designs where the amount of toner to be filled into the cartridge is minimized so that the toner is used up at the time of cartridge replacement, the toner is repeatedly subjected to mechanical stress, making the problem particularly significant.

[0004] In view of the above, Japanese Patent No. 5223382 proposes a method to suppress the detachment of external additives from the surface of toner particles and the rolling of external additives on the surface of toner particles by using hemispherical, large-diameter fine particles as external additives in toners. However, hollow hemispherical organic fine particles are generated by breaking the hollow organic fine particles to remove the internal gas. Therefore, under conditions where strong external force is applied to the fine particles, the reduction of toner function due to the breakage of the fine particles themselves becomes a problem. In addition, the fine particles have a shape that retains air within the hemisphere, so the low-temperature fixing performance of the toner is problematic due to the heat insulation effect of the air.

[0005] Furthermore, Japanese Patent No. 3943781 discloses a method for obtaining a toner with excellent development and transfer properties even after long-term use by forming a silicon compound coating layer on the surface of toner particles. However, compared to fine-particle external additives, the high surface coverage of the toner particles cannot be ignored as an obstacle to the fixing properties of the toner. Summary of the Invention

[0006] The purpose of this invention is to provide toners, toner additives, and fine particles that have excellent low-temperature fixing properties and can maintain their initial cleanliness even after continuous mechanical stress.

[0007] The present invention relates to a toner comprising: toner particles containing a binder resin and a colorant; and fine particles on the surface of the toner particles, wherein the fine particles are solid and generally hemispherical, and have a generally flat surface and a curved surface, and wherein the average number of the longest diameters “w” of the generally flat surface is 10 to 400 nm.

[0008] The present invention also relates to an external additive for toners, which is solid and generally hemispherical, and has a generally flat surface and a curved surface, wherein the average number of the longest diameter "w" of the generally flat surface is 10 to 400 nm.

[0009] The present invention also relates to fine particles that are solid and generally hemispherical, and have a generally flat surface and a curved surface, wherein the average number of the longest diameter “w” of the generally flat surface is 10 to 400 nm.

[0010] Further features of the invention will become apparent from the following description of exemplary embodiments, with reference to the accompanying drawings. Attached Figure Description

[0011] Figure 1 This is a diagram used to illustrate an example of a roughly hemispherical shape.

[0012] Figure 2A , Figure 2B , Figure 2C and Figure 2D This is a diagram used to illustrate an example of the maximum length df, maximum height "h", and maximum width "b" when observing a cross-section of a roughly hemispherical fine particle or toner with an external additive.

[0013] Figure 2E , Figure 2F , Figure 2E 'and Figure 2F ′ is a diagram used to illustrate an example of the major axis l1 of ellipse e1, the major axis l2 of ellipse e2, the minor axis s1 of ellipse e1, and the minor axis s2 of ellipse e2 when observing a cross-section of a generally hemispherical fine particle or toner with an external additive.

[0014] Figure 3 This is a diagram used to illustrate an example of the longest diameter "w" when viewed from any direction as a roughly hemispherical fine particle or toner with an external additive.

[0015] Figure 4 This is a diagram used to illustrate an example of the angle of approximately hemispherical fine particles when viewed from the side. Detailed Implementation

[0016] Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0017] In this invention, unless otherwise stated, the description of a numerical range, “○○ to ××”, refers to a numerical range that includes the lower limit and the upper limit as endpoints.

[0018] The present invention relates to a toner comprising: toner particles containing a binder resin and a colorant; and fine particles on the surface of the toner particles, wherein the fine particles are solid and generally hemispherical, and have a generally flat surface and a curved surface, and wherein the average number of the longest diameters “w” of the generally flat surface is 10 to 400 nm.

[0019] The present invention also relates to an external additive for toners, which is solid and generally hemispherical, and has a generally flat surface and a curved surface, wherein the average number of the longest diameter "w" of the generally flat surface is 10 to 400 nm.

[0020] The present invention also relates to fine particles that are solid and generally hemispherical, and have a generally flat surface and a curved surface, wherein the average number of the longest diameter “w” of the generally flat surface is 10 to 400 nm.

[0021] Essentially, the toner of the present invention has fine particles on the surface of the toner particles containing binder resin and colorant, and the fine particles are solid and generally hemispherical.

[0022] Furthermore, it is necessary that the external additives used in the colorant of the present invention are solid and generally hemispherical.

[0023] Furthermore, it is essential that the fine particles of the present invention are solid and generally hemispherical.

[0024] As used in this article, the term "solid" refers to a state where the interior of a fine particle is completely filled with solid material and is therefore not hollow. This can be confirmed by observing the cross-section of the fine particle.

[0025] When the fine particles are solid, even when they are continuously subjected to mechanical stress on the surface of the toner particles, they can remain on the surface of the toner particles without disrupting their approximately hemispherical shape. A typical example of this continuous mechanical stress on the fine particles is a design in which the amount of toner to be filled into the cartridge is minimized so that the toner is used up at the time of cartridge replacement (hereinafter also referred to as a "toner depletion design"). In a toner depletion design, the frequency of repeating the cycle of developing the same toner particles and returning them to the cartridge without development increases when the amount of toner in the cartridge is low, i.e., near the time of cartridge replacement. Therefore, the toner is repeatedly subjected to mechanical stress. Even in this state, as long as the fine particles are solid, they can remain on the surface of the toner particles without disrupting their approximately hemispherical shape; therefore, the initial cleanliness of the toner, one of the effects of this invention, can be maintained.

[0026] Furthermore, when the fine particles are solid, there is no air inside them, so heat conduction during toner fixing is not hindered by the insulating effect of air. It is well known that the thermal conductivity of air is 0.023 [W / (m·K)], while, for example, the thermal conductivity of silicone resin is 0.13 to 0.14 [W / (m·K)], and that of silica is 1.38 [W / (m·K)]. Therefore, when fine particles are present on the surface of the toner particles, heat is transferred faster in solid fine particles filled with solid material than in hollow fine particles. As a result, the fine particles contribute to the low-temperature fixing properties of the toner.

[0027] In addition, in this invention, the fine particles present on the surface of the toner particles are required to be approximately hemispherical and have a generally flat surface and curved surface.

[0028] Furthermore, in another aspect of the invention, the external additive for the colorant is required to be generally hemispherical and have a generally flat surface and curved surface.

[0029] Furthermore, in another aspect of the invention, the fine particles are required to be generally hemispherical and have generally flat and curved surfaces.

[0030] When the fine particles or external additives for toner are approximately hemispherical and have a generally flat and curved surface, they adhere to the surface of the toner particles in such a manner that the generally flat surface of the fine particles or external additives contacts the surface of the toner particles. Therefore, the migration of the fine particles or external additives from the surface of the toner particles and their rolling on the surface of the toner particles are suppressed. As a result, the initial cleanliness of the toner can be maintained even when the fine particles or external additives present on the surface of the toner particles are repeatedly subjected to mechanical stress.

[0031] Furthermore, when the fine particles or toner external additive are approximately hemispherical and have a generally flat and curved surface, the curved surface of the fine particles or toner external additive adhered to the surface of the toner particles serves as the surface that abuts against the component. Therefore, the contact area between the component and the toner particles is reduced, thus minimizing the adhesion between them. For example, when the component is a photosensitive drum, the reduced adhesion between the photosensitive drum and the toner particles improves the transferability of the toner. As a result, the amount of residual toner transferred is reduced, thus exhibiting an improved initial cleanliness.

[0032] As used in this article, the term "roughly hemispherical" refers to a shape obtained by cutting an ellipsoid along any face of the ellipsoid. Figure 1 As shown, when an ellipsoid is divided into two three-dimensional objects along an arbitrary surface, one of the three-dimensional objects (in...) Figure 1 In this invention, a generally hemispherical example (a three-dimensional object represented by a dot pattern) is used. In this invention, an ellipsoid includes three-dimensional objects that are true spheres and approximately ellipsoids, and any face may or may not pass through the center of the ellipsoid. The method for manufacturing generally hemispherical fine particles or toner additives described herein is not limited to methods involving cutting ellipsoids, but also includes, for example, methods involving forming fine particles or toner additives in a bottom-up manner on a substrate having a generally flat surface. In the case of a method involving forming fine particles or toner additives in a bottom-up manner on a substrate having a generally flat surface, when using particles having a generally flat surface and a particle size tens of times larger than the size of the fine particles or toner additive as the substrate, generally hemispherical fine particles or toner additives with generally flat surfaces and curved surfaces can be easily manufactured.

[0033] The fact that fine particles or external additives for colorants are generally hemispherical can be confirmed by observing the cross-sections intersecting the generally flat surfaces of the fine particles or external additives for colorants. Specifically, when observing the cross-section of the fine particles or external additives for toners, the following two points are satisfied to determine that the fine particles or external additives are approximately hemispherical: (1) When, in the cross-section intersecting the approximately flat surface of the fine particles or external additives for toners, the line connecting the two intersection points Pa and Pb of the line Lf originating from the approximately flat surface and the line Lc originating from the curved surface is defined as the imaginary line Li, and the longest distance between the imaginary line Li and the line Lf originating from the approximately flat surface is defined as the maximum length df, in the line Ls1 that intersects the imaginary line Li perpendicularly on the cross-section, the maximum height “h” is defined as the maximum distance between the distance Da between point Pc and point Pe and the distance Db between point Pd and point Pe, where point Pc is the intersection point of the imaginary line Li and the line Ls1, point Pe is the intersection point of the line Lc originating from the curved surface and the line Ls1, and point Pd is the intersection point of the line Lc originating from the approximately flat surface and the line Lc originating from the curved surface. When the intersection of line Lf and line Ls1 on the surface of the flat surface, and point Pe is the intersection of line Lc and line Ls1 originating from the curved surface, the average number of the ratios of the maximum length df to the maximum height "h" df / h is 0.00 to 0.10; and (2) when, in a cross section intersecting with a generally flat surface of fine particles or external additives for toners, an ellipse passing through two intersections of the generally flat surface and the curved surface and circumscribed with the curved surface of fine particles or external additives for toners is represented by e1, and an ellipse passing through two intersections of the generally flat surface and the curved surface and circumscribed with the curved surface of fine particles or external additives for toners is represented by e2, the average number of the ratios of the major axis l1 of ellipse e1 to the major axis l2 of ellipse e2 l1 / l2 is 0.90 to 1.10, and the average number of the ratios of the minor axis s1 of ellipse e1 to the minor axis s2 of ellipse e2 s1 / s2 is 0.90 to 1.10. Instances of maximum length df and maximum height "h" are shown in Figures 2A to 2D The average number of particles with a density of df / h is preferably 0.00 to 0.05, because fine particles or toners are more strongly adhered to the surface of the toner particles by external additives, thus improving the cleanliness of the toner after continuous mechanical stress. Examples of ellipses e1, e2, the major axis l1 of e1, the major axis l2 of e2, the minor axis s1 of e1, and the minor axis s2 of e2 are shown in [reference needed]. Figures 2E to 2F 'middle.

[0034] Furthermore, in the toner of the present invention, the fine particles present on the surface of the toner particles have a generally flat surface and a curved surface, and the average number of the longest diameter "w" of the generally flat surface is 10 to 400 nm.

[0035] Furthermore, in another aspect of the invention, the external additive for the colorant has a generally flat surface and a curved surface, and the average number of the longest diameter "w" of the generally flat surface is 10 to 400 nm.

[0036] Furthermore, in another aspect of the invention, the fine particles have a generally flat surface and a curved surface, and the average number of the longest diameter "w" of the generally flat surface is 10 to 400 nm.

[0037] The longest diameter "w" of a generally flat surface of a fine-particle or toner external additive is calculated as follows: The fine-particle or toner external additive is viewed from above (the direction from which the generally flat surface of the fine-particle or toner external additive can be observed), and the longest diameter is the distance between the longest straight lines connecting any two points on the outer perimeter of the generally flat surface. An example of the longest diameter "w" is shown below. Figure 3 middle.

[0038] When the average number of longest diameters "w" on the generally flat surface of the fine particles or toner external additives is between 10 and 400 nm, the initial cleanliness and low-temperature fixing properties of the toner become satisfactory. When the average number of longest diameters "w" is 10 nm or more, the probability of fine particles or toner external additives present on the surface of the toner particles (not the surface of the toner particles) coming into contact with the component increases. Therefore, when the average number of longest diameters "w" is 10 nm or more, the adhesion of the toner particles to the component can be kept small. As a result, the amount of residual toner in the transfer is reduced, thus showing a favorable effect on initial cleanliness. When the average number of longest diameters "w" is 30 nm or more, preferably 50 nm or more, a further effect on initial cleanliness is shown. Furthermore, when the average number of longest diameters "w" is 400 nm or less, it is possible to prevent the area of ​​the toner particle surface covered by a single fine particle or a single toner external additive particle from becoming too large, thus obtaining a favorable effect on the low-temperature fixing properties of the toner. The average number of longest diameter "w" segments being less than 300 nm, preferably less than 250 nm, is more effective for the low-temperature fixing properties of the toner.

[0039] The average number of shapes and longest diameter "w" of the external additives for fine particles or toners can be controlled by the type and amount of monomers used in the manufacture of the external additives for fine particles or toners, the reaction temperature, reaction time, reaction medium, pH of the reaction system, and the type and concentration of the dispersant. Furthermore, when the external additives for fine particles or toners are manufactured by a method comprising forming the fine particles or external additives on a substrate in a bottom-up manner, the average number of shapes and longest diameter "w" of the external additives for fine particles or toners can also be controlled by the shape and size of the substrate.

[0040] In the toner of the present invention, when observing the surface of the toner particles, it is preferable to observe the generally flat surface of the fine particles.

[0041] When observing the surface of the toner particles, if the fine particles have a generally flat surface, some of the fine particles become prone to migrating from the surface of the toner particles to the surface of the component. The fine particles that migrate to the surface of the component adhere to the surface of the component in such a way that their generally flat surfaces come into contact with each other. For example, when the component is a cleaning squeegee, some of the fine particles that migrate to the cleaning squeegee adhere to the surface of the cleaning squeegee in such a way that their generally flat surfaces come into contact with each other. Therefore, the curved surface of the fine particles on the cleaning squeegee serves as the contact surface with the photosensitive drum. As a result, the torque during drum cleaning is reduced, and therefore, almost no toner particle escape occurs. Thus, initial cleaning performance is improved.

[0042] Because of the generally hemispherical shape of the fine particles or external additives for toners in this invention, most of the fine particles or external additives for toners are fixed to the surface of the toner particles in such a way that their generally flat surfaces can contact each other. Therefore, migration of the fine particles or external additives from the surface of the toner particles is suppressed. However, since there is no network between the particles of the fine particles or external additives for toners, and no chemical bonds exist between the fine particles or external additives for toners and the toner particles, some fine particles or external additives for toners migrate from the surface of each toner particle to the surface of the component. The observation of a generally flat surface of the fine particles or external additives for toners when observing the surface of the toner particles means that not all the fine particles or external additives for toners are fixed to the surface of the toner particles in such a way that their generally flat surfaces contact each other, but rather that a portion of the fine particles or external additives for toners can migrate from the surface of the toner particles to the surface of the component. In this state, fine particles migrating to the surface of the component or external additives for the toner help improve initial cleanliness, and fine particles or external additives for the toner adhering to the surface of each toner particle help maintain initial cleanliness. As a result, good cleanliness can be achieved when the toner is repeatedly subjected to mechanical stress.

[0043] In the toner of the present invention, when the surface of the toner particles is viewed from any direction and the angle of each fine particle is defined as 0° when the substantially flat surface of the fine particles is in contact with the surface of each toner particle, fine particles having an angle greater than 90° and less than 270° are fine particles whose substantially flat surfaces are observed. In the toner of the present invention, when 1.0% or more of the fine particles present on the surface of the toner particles are fine particles whose substantially flat surfaces are observed, it is determined that a substantially flat surface of fine particles is observed. An example of the angle of the fine particles when the surface of the toner particles is viewed laterally is shown in... Figure 4 From the viewpoint of component contamination, the proportion of fine particles observed on a generally flat surface is preferably 40.0% or less. This is because when the proportion of fine particles observed on a generally flat surface is 40.0% or less, the balance between fine particles adhering to the surface of the toner particles and fine particles adhering to the surface of the component becomes good, thus improving the cleanliness of the toner after repeated exposure to mechanical stress. More preferably, the proportion of fine particles observed on the surface of the toner particles on a generally flat surface is 20.0% or less.

[0044] When observing the surface of toner particles, the proportion of fine particles with a generally flat surface can be controlled by the shape of the fine particles, the number of fine particles added externally to the toner, and the external addition conditions. As mentioned above, the shape of the fine particles can be controlled by the type and number of monomers in the fine particles, the reaction temperature, reaction time, reaction medium and pH of the reaction system, the type and concentration of the dispersant, and the shape and size of the substrate during the manufacture of the fine particles.

[0045] Furthermore, the toner of the present invention preferably satisfies the following: when observing a cross section intersecting a generally flat surface with fine particles present on the surface of the toner particles, the straight line connecting the two intersection points Pa and Pb of the line Lf originating from the generally flat surface and the line Lc originating from the curved surface is defined as an imaginary straight line Li; in the straight line Ls1 that intersects the imaginary straight line Li perpendicularly, the maximum height “h” is defined as the distance between point Pc and point Pe, which is the largest distance between point Pd and point Pe, and the distance between point Pd and point Pe, which is the largest distance between point Pc and point Pe, where point Pc is the intersection point of the imaginary straight line Li and the straight line Ls1, point Pe is the intersection point of the line Lc and the straight line Ls1, and point Pd is the intersection point of the line Lf and the straight line Ls1; and in the straight line Ls2 that is parallel to the imaginary straight line Li, the maximum width “b” is defined as the distance between the two intersection points Pf and Pg of the straight line Ls2 and the line Lc, which is the largest distance between point Pf and point Pg, which is the largest distance between point Pf and point Pg, and the maximum width “b”, the average number of ratios h / b of the maximum height “h” to the maximum width “b” is 0.33 to 0.80.

[0046] Furthermore, in another aspect of the present invention, the external additive for the toner preferably satisfies the following: when observing a cross section intersecting the generally flat surface of the external additive for the toner, the straight line connecting the two intersection points Pa and Pb of the line Lf originating from the generally flat surface and the line Lc originating from the curved surface is defined as an imaginary straight line Li; in the straight line Ls1 that intersects the imaginary straight line Li perpendicularly, the maximum height “h” is defined as the distance between point Pc and point Pe, which is the maximum distance between point Pd and point Pe, and the maximum height “h” is defined as the distance between point Pc and point Pe, which is the intersection point of the imaginary straight line Li and the straight line Ls1, point Pe is the intersection point of the line Lc and the straight line Ls1, and point Pd is the intersection point of the line Lf and the straight line Ls1; and in the straight line Ls2 that is parallel to the imaginary straight line Li, the maximum width “b” is defined as the distance between the two intersection points Pf and Pg of the straight line Ls2 and the line Lc, which is the maximum distance h / b.

[0047] Furthermore, in another aspect of the invention, the fine particles preferably satisfy the following: when observing a cross section intersecting the generally flat surface of the fine particles, the straight line connecting the two intersection points Pa and Pb of the line Lf originating from the generally flat surface and the line Lc originating from the curved surface is defined as an imaginary straight line Li; in the straight line Ls1 that intersects the imaginary straight line Li perpendicularly, the maximum height “h” is defined as the distance between point Pc and point Pe, which is the largest distance between point Pd and point Pe, and the distance between point Pd and point Pe, which is the largest distance between the imaginary straight line Li and the straight line Ls1, point Pe is the intersection point between the line Lc and the straight line Ls1, and point Pd is the intersection point between the line Lf and the straight line Ls1; and in the straight line Ls2 that is parallel to the imaginary straight line Li, the maximum width “b” is defined as the distance between the two intersection points Pf and Pg of the straight line Ls2 and the line Lc, which is the largest distance, the average number of ratios h / b of the maximum height “h” to the maximum width “b” is 0.33 to 0.80.

[0048] When observing the cross-section of fine particles or external additives for toners, the ratio h / b is calculated by measuring the maximum height "h" and maximum width "b" within a single fine particle or external additive particle. Examples of maximum height "h" and maximum width "b" are shown below. Figures 2A to 2D middle.

[0049] When the average number of toner particles with a ratio (h / b) of maximum height "h" to maximum width "b" is between 0.33 and 0.80, the toner exhibits better cleanliness and low-temperature fixing properties under continuous mechanical stress. When the average number of h / b particles is above 0.33, the area of ​​fine particles adhering to the surface of the toner particles or the area of ​​the toner external additive in contact with the component can be reduced. Furthermore, the distance between the toner particles and the component can be kept constant. As a result, the adhesion between the toner particles and the component is reduced, thus suppressing the amount of residual toner in the transfer. Therefore, the initial cleanliness of the toner is superior. Additionally, the area of ​​the toner particle surface covered by a single fine particle or a single toner external additive particle can be suppressed, thus achieving a more favorable effect on low-temperature fixing properties. Furthermore, when the average h / b ratio is 0.80 or less, even when fine particles or external additives for toner present on the surface of the toner particles are repeatedly subjected to mechanical stress, the fine particles or external additives for toner can remain adhered to the surface of the toner particles. As a result, the migration of fine particles or external additives for toner to the component is suppressed, thus further enhancing the maintenance of cleanliness when fine particles or external additives for toner are continuously subjected to mechanical stress.

[0050] The average number of h / b ratios can be controlled by the type and amount of monomers used as fine particles or colorants as external additives, the reaction temperature, reaction time, reaction medium and pH of the reaction system during monomer polymerization, and the type and concentration of the dispersant used for the monomers in the reaction system.

[0051] In this invention, the fine particles present on the surface of the toner particles preferably comprise at least one of the structures selected from the group consisting of the following formulas (D), (T), and (Q):

[0052] (Ra)(Rb)Si(O 1 / 2 Equation (D)

[0053] Rc-Si(O 1 / 2 Formula 3 (T)

[0054] Si(O 1 / 2 Formula 4 (Q)

[0055] In formulas (D), (T), and (Q), Ra, Rb, and Rc each represent an organic group bonded to silicon.

[0056] In another aspect of the invention, the external additive for the colorant preferably includes at least one of the structures selected from the group consisting of formulas (D), (T), and (Q).

[0057] In another aspect of the invention, the fine particles preferably comprise at least one of the structures selected from the group consisting of formulas (D), (T), and (Q).

[0058] When fine particles or toners are combined with external additives comprising at least one of the structures selected from the group consisting of formulas (D), (T), and (Q), the initial cleanliness becomes better.

[0059] In each of formulas (D), (T), and (Q), 0 to 2 of the four valence electrons of the Si atom participate in bonding with Ra, Rb, and Rc, and the remaining 2 to 4 valence electrons participate in bonding with the O atom. The O atom forms a state where each of its two valence electrons participates in bonding with Si, i.e., a siloxane bond (Si-O-Si). Two Si atoms share one O atom, therefore the siloxane polymer site formed by the siloxane bond is represented as -Si(O 1 / 2 ) * (Where * represents an integer from 2 to 4). As the integer represented by * increases, the number of siloxane bonds increases, thus maintaining a low surface free energy for the fine particles or toner external additive. Simultaneously, the organic groups represented by any of Ra, Rb, and Rc exhibit hydrophobicity, therefore the presence of any of Ra, Rb, and Rc also reduces the surface free energy of the fine particles or toner external additive. In this invention, the fine particles or toner external additive adhered to the surface of the toner particles abut against the component, thus the reduction in the surface free energy of the fine particles or toner external additive maintains a low adhesion between the fine particles or toner external additive and the component. Therefore, when the fine particles or toner external additive includes at least one structure selected from the group consisting of formulas (D), (T), and (Q), the toner's transferability becomes good, thereby having a favorable effect on its initial cleanability. More preferably, the fine particles or toner external additive includes a structure represented by formula (T). In this case, the balance between the siloxane polymer sites and organic groups of the external additives for fine particles or toners becomes appropriate, thereby exerting a further effect on the initial cleaning properties.

[0060] Ra, Rb, and Rc each preferably represent an organic group having 1 to 8 carbon atoms (preferably 1 to 6), more preferably a hydrocarbon group, and even more preferably an alkyl group.

[0061] Furthermore, the content of the structure represented by formula (D), formula (T) and / or (Q) in the external additive for fine particles or toners of the present invention is preferably 50 mol% or more, more preferably 70 mol% or more.

[0062] The siloxane polymer site (-Si(O)) in each structure represented by formulas (D), (T), and (Q) 1 / 2) * (Where * represents an integer from 2 to 4) can be achieved through the presence of fine particles or toners using external additives. 29 The presence of Ra, Rb, and Rc in formulas (D) and (T) can be confirmed by using external additives such as fine particles or toners. 13 This was confirmed by C-NMR measurements.

[0063] The toner of the present invention preferably comprises approximately hemispherical fine particles on the surface of the toner particles, comprising 0.1 parts by weight or more relative to 100 parts by weight of toner particles. This is because the toner exhibits good low-temperature fixing properties and good cleanliness before and after continuous mechanical stress, thus enhancing the effects of the present invention. Furthermore, from the viewpoint of low-temperature fixing properties, the toner preferably comprises approximately hemispherical fine particles on the surface of the toner particles, comprising less than 4.0 parts by weight relative to 100 parts by weight of toner particles. Moreover, from the viewpoint of preventing contamination of components, the toner preferably comprises approximately hemispherical fine particles on the surface of the toner particles, comprising less than 3.0 parts by weight relative to 100 parts by weight of toner particles.

[0064] The external additive for fine particles or toners of the present invention preferably comprises at least one product selected from the group consisting of condensation products of organosilicon compounds having structures represented by formulas (ZD), (ZT), and (ZQ):

[0065]

[0066] In formulas (ZD), (ZT), and (ZQ), Ra, Rb, and Rc each represent an organic group bonded to silicon, and R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 and R 9 Each can be independently represented by a halogen atom, hydroxyl group, acetoxy group, or alkoxy group.

[0067] Polycondensation of organosilicon compounds having any one of Ra, Rb, and Rc can improve the hydrophobicity of fine particles or external additives for toners, thereby enabling the toner to exhibit excellent initial cleanliness. Ra, Rb, and Rc have the same meaning as Ra, Rb, and Rc in the structures represented by formulas (D), (T), and (Q), respectively, and each preferably represents an organic group having 1 to 8 carbon atoms (preferably 1 to 6), more preferably a hydrocarbon group, and even more preferably an alkyl group.

[0068] In addition, R 1 R2 R 3 R 4 R 5 R 6 R 7 R 8 and R 9 Each group independently represents a halogen atom, hydroxyl group, acetoxy group, or alkoxy group (these groups are collectively referred to as "reactive groups" below). These reactive groups undergo hydrolysis, addition polymerization, and condensation polymerization to form cross-linked structures, thus yielding fine particles or external additives for toners with excellent durability. From the viewpoint of the stable hydrolysis at room temperature and the properties of fine particles or external additives deposited on the substrate, R... 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 and R 9 Each is preferably represented by an alkoxy group, more preferably a methoxy group, and / or an ethoxy group. R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 and R 9 Hydrolysis, addition polymerization, and condensation polymerization can be controlled by reaction temperature, reaction time, reaction medium, and pH of the reaction system.

[0069] The content of the condensation product of the organosilicon compound having a structure represented by formula (ZD), formula (ZT), and / or formula (ZQ), obtained as a result of hydrolysis, addition polymerization, and condensation polymerization in the fine particles or external additives, is preferably 50 mol% or more, more preferably 70 mol% or more. Furthermore, it is more preferable that the fine particles or external additives include the condensation product of the organosilicon compound having a structure represented by formula (ZT), because, as mentioned above, the balance between the siloxane polymer site and the organic group in the fine particles or external additives becomes suitable.

[0070] To obtain fine particles or external additives for toners, it is desirable to use, alone or in combination, two reactive groups (R0 and Rb) in the molecule, in addition to Ra and Rb in formula (ZD). 1 and R 2 Organosilicon compounds (bifunctional silanes) that, except for Rc in formula (ZT), have three reactive groups (R) in their molecules. 3 R 4 and R 5Organosilicon compounds (trifunctional silanes) and molecules having four reactive groups (R) in formula (ZQ) 6 R 7 R 8 and R 9 Organosilicon compounds (tetrafunctional silanes).

[0071] Examples of organosilicon compounds having a structure represented by formula (ZD) include dimethyldimethoxysilane, dimethyldiethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane.

[0072] Examples of organosilicon compounds having a structure represented by formula (ZT) include trifunctional vinylsilanes, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyltriacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane. Vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, and vinyldiethoxyhydroxysilane; trifunctional allylsilanes, such as allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, allylethoxydimethoxysilane, allyltrichlorosilane, allylmethoxydichlorosilane, allylethoxydichlorosilane, allyldimethoxychlorosilane, allylmethoxyethoxychlorosilane, allyldiethoxychlorosilane, allyltriacetoxysilane, allyldiacetoxymethoxysilane, allyldiacetoxyethoxysilane, allylacetoxydimethoxysilane, allyltriacetoxysilane, allylacetoxydimethoxysilane, allyltriacetoxysilane, allylethoxydichlorosilane, allyltriacetoxysilane, allylacetoxydimethoxysilane, allyltriacetoxysilane, allylethoxydiacetoxysilane, allyltriacetoxysilane, allyltriacetoxymethoxysilane, allyltriacetoxysilane, allyltriacetoxymethoxysilane, allyltriacetoxysilane, allyltriacetoxydimethoxysilane, allyltriacet ... Acyloxymethoxyethoxysilanes, allylacetoxydiethoxysilanes, allyltrihydroxysilanes, allylmethoxydihydroxysilanes, allylethoxydihydroxysilanes, allyldimethoxyhydroxysilanes, allylethoxymethoxyhydroxysilanes, and allyldiethoxyhydroxysilanes; trifunctional styrylsilanes, such as p-styryltrimethoxysilane; trifunctional methylsilanes, such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, and methyltriacetoxysilane. , methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane and methyldiethoxyhydroxysilane; trifunctional ethylsilanes, such as ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane and ethyltrihydroxysilane; trifunctional propylsilanes, such as propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane and propyltrihydroxysilane;Trifunctional butylsilanes, such as butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, and butyltrihydroxysilane; trifunctional hexylsilanes, such as hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, and hexyltrihydroxysilane; and trifunctional phenylsilanes, such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane; trifunctional epoxysilanes, such as 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; trifunctional methacryloylsilanes, such as 3-methacryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltriethoxysilane. Silanes; trifunctional acryloylsilanes, such as 3-acryloyloxypropyltrimethoxysilane; trifunctional aminosilanes, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; trifunctional ureosilanes, such as 3-ureopropyltriethoxysilane; trifunctional 3-chloropropylsilanes, such as 3-chloropropyltrimethoxysilane; trifunctional mercaptosilanes, such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; trifunctional thiosilanes, such as bis(triethoxysilylpropyl)tetrasulfide; and trifunctional isocyanate silanes, such as 3-isocyanate propyltriethoxysilane.

[0073] Examples of organosilicon compounds having a structure represented by formula (ZQ) include: tetraalkoxysilanes, such as tetramethoxysilane and tetraethoxysilane; tetraalkylcarboxysilanes, such as tetraacetoxysilane; and tetrahalosilanes, such as tetrachlorosilane.

[0074] In addition to the condensation products of organosilicon compounds having structures represented by formula (ZD), formula (ZT), and / or formula (ZQ), external additives for fine particles or toners may also include any one of the condensation products of organosilicon compounds having one reactive group in their molecules (monofunctional silanes), difunctional silanes, trifunctional silanes, and tetrafunctional silanes other than those mentioned above. Examples include the following.

[0075] Hexamethyldisilane, trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, tert-butyldimethylchlorosilane, N,N'-bis(trimethylsilyl)urea, N,O-bis(trimethylsilyl)trifluoroacetamide, trimethylsilyl trifluoromethanesulfonate, 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane, trimethylsilylacetylene, hexamethyldisilane, tetraisocyanate silane, methyltriisocyanate silane, and vinyltriisocyanate silane.

[0076] In addition to condensation products of organosilicon compounds having structures represented by formula (ZD), formula (ZT) or formula (ZQ), external additives for fine particles or toners may also include either condensation products of organotitanium compounds or organoaluminum compounds.

[0077] Examples of organotitanium compounds include titanium methoxide, titanium ethanol, titanium n-propoxide, titanium tetraisopropoxy, titanium tetra-n-butoxy, titanium isobutoxide, titanium butoxide dimer, titanium tetra-2-ethylhexanol, titanium diisopropoxybis(acetylacetone), titanium tetraacetylacetone, titanium di-2-ethylhexoxybis(2-ethyl-3-hydroxyhexoxy), titanium diisopropoxybis(ethyl acetoacetate), titanium tetra(2-ethylhexoxy), titanium diisopropoxy-bis(acetylacetone), titanium lactate, titanium isopropoxide methacrylate, titanium triisopropoxy titanate, titanium methoxypropoxide, and titanium stearyl alcohol.

[0078] Examples of organoaluminum compounds include aluminum n-butoxide (III), aluminum sec-butoxide (III), aluminum sec-butoxide (III) bis(ethyl acetoacetate), aluminum tert-butoxide (III), aluminum disec-butoxide (III) ethyl acetoacetate, aluminum diisopropoxide (III) ethyl acetoacetate, aluminum ethoxide (III), aluminum hexafluoroglutarate, aluminum 3-hydroxy-2-methyl-4-pyranoate (III), aluminum isopropoxide (III), aluminum 9-octadecenylacetoacetate diisopropoxide, aluminum 2,4-glutarate (III), aluminum phenolate, and aluminum 2,2,6,6-tetramethyl-3,5-heptanoate (III).

[0079] These organosilicon compounds, organotitanium compounds, and organoaluminum compounds can be used alone or in combination.

[0080] The following describes a specific manufacturing method for the external additives used in fine particles or colorants according to the present invention, but the manufacturing method is not limited thereto.

[0081] The manufacturing method for fine particles or toners using external additives is, for example, the sol-gel method. The sol-gel method involves using a metal alkoxide M(OR)n (M: metal, O: oxygen, R: hydrocarbon, n: oxidation number of the metal) as a starting material, and the metal alkoxide undergoes hydrolysis and condensation in a medium to gel through a sol state. When the fine particles or toners used as external additives include structures represented by formulas (D), (T), or (Q), only organosilicon compounds having structures represented by formulas (ZD), (ZT), or (ZQ) are needed as the metal alkoxide M(OR)n. This method is used to synthesize glasses, ceramics, organic-inorganic hybrids, or nanocomposites. When using this manufacturing method, functional materials of various shapes, such as surface layers, fibers, bulk materials, and fine particles, can be produced from the liquid phase at low temperatures. Furthermore, in the sol-gel method, because a solution is used as a starting material and the material is formed by gelling the solution, various microstructures and shapes can be produced. The fine structure and shape can be adjusted by, for example, the type and amount of monomers, reaction temperature, reaction time, reaction medium and pH of the reaction system, as well as the type and concentration of dispersant.

[0082] Typically, it is known that in sol-gel reactions, the bonding state of the metal-oxoalkane bond (MOM) to be formed varies depending on the acidity of the reaction medium. Specifically, when the reaction medium is acidic, hydrogen ions electrophilically add to the oxygen atom of a reactive group (e.g., an alkoxy group). The oxygen atom in the water molecule then coordinates with the metal atom to form a hydroxyl group through a substitution reaction. When water is sufficiently present, a hydrogen ion attacks an oxygen atom of the reactive group (e.g., an alkoxy group). Therefore, as the amount of hydrogen ions and reactive groups in the medium decreases as the reaction proceeds, the substitution reaction to form the hydroxyl group slows down. Thus, polycondensation occurs before all the reactive groups bound to the metal atom undergo hydrolysis, thereby relatively easily producing one-dimensional linear polymers or two-dimensional polymers.

[0083] Simultaneously, in an alkaline medium, hydroxide ions add to the metal atom to form a five-coordinate intermediate. Therefore, all reactive groups (e.g., alkoxy groups) readily decouple and are easily replaced by hydroxyl groups. In particular, when metal compounds with three or more reactive groups in the same metal atom are used, three-dimensional hydrolysis and condensation occur, resulting in organometallic polymers with numerous three-dimensional cross-links. Furthermore, the reaction is completed in a short time.

[0084] Therefore, in order to form fine particles or external additives for toners made of organometallic polymers, it is preferable to carry out the sol-gel reaction in an alkaline state. When manufacturing fine particles or external additives for toners in an aqueous medium, specifically, it is preferable to carry out the reaction at a pH of 8.0 or higher. Therefore, it is possible to form fine particles or external additives for toners with higher strength and superior durability.

[0085] Examples of aqueous media include: water; and mixed solvents of water and alcohols such as methanol, ethanol, or propanol.

[0086] In addition, in order to make the fine particles or toners of the present invention have a solid and generally hemispherical shape, and to control the average number of the longest diameter "w" of their generally flat surface to be 10 to 400 nm, it is preferable to manufacture them by dispersing organometallic compounds and substrates in a medium.

[0087] First, the substrate is dispersed in a medium to obtain a substrate dispersion. It is preferable to disperse the substrate at a concentration of 5 to 40% by mass of solid content relative to the total amount of the substrate dispersion. A dispersion stabilizer, described later, may be used appropriately. Furthermore, it is preferable to adjust the temperature of the substrate dispersion to 35°C or higher. Additionally, it is preferable to adjust the pH of the substrate dispersion to a pH at which the condensation of organometallic compounds is difficult to occur. Although the pH at which the condensation of organometallic compounds is difficult to occur varies depending on the type of organometallic compound, it is preferable to adjust the pH of the substrate dispersion to a range of ±0.5 centered at the pH at which the reaction is most difficult to occur. Complete dispersion of the substrate in the medium is not necessary. For example, when the substrate is a plate, the following can be performed: the plate is erected in a reaction vessel, and condensation occurs on the substrate.

[0088] Next, the organometallic compound is preferably hydrolyzed before use. For example, the organometallic compound can be hydrolyzed in other containers. Regarding the concentration added during hydrolysis, when the amount of the organometallic compound is set to 100 parts by mass, the amount of water from which ionic components have been removed (e.g., ion-exchanged water or RO water) is preferably 40 to 500 parts by mass, and more preferably 100 to 400 parts by mass. Hydrolysis is preferably carried out under conditions of pH 1.0 to 7.0, temperature 15 to 80°C, and time 1 to 600 minutes.

[0089] Then, the hydrolyzed organometallic compound is added to the substrate dispersion. The substrate dispersion and the hydrolysate of the organometallic compound are stirred and mixed, and the mixture is preferably maintained at 35°C or above for 3 to 120 minutes. Afterward, the pH of the mixture is adjusted to a pH suitable for the condensation of the organometallic compound (preferably pH 6.0 or above, or pH 3.0 or below, more preferably pH 8.0 or above) so that the organometallic compound can condense in one gaseous manner. The resulting product is then preferably maintained at 35°C or above for 60 minutes or more. Thus, fine particles formed from organometallic polymers, such as organosilicon polymers, or external additives for colorants are formed on the surface of the substrate.

[0090] Then, the substrate with fine particles or external additives for colorant formation on its surface is stirred and mixed with a medium that has high solubility for the substrate but low solubility for the fine particles or external additives for colorant, thereby dissolving only the substrate. Solubility varies depending on the material of the substrate and the type of medium; therefore, the solid content concentration of the substrate, stirring time, and stirring temperature are set within a range that allows for sufficient dissolution of the substrate. The fine particles or external additives for colorant are then separated by methods such as centrifugation and dried. Thus, solid, approximately hemispherical fine particles are obtained. When the solubility of the substrate is low, the fine particles or external additives for colorant can be separated by: lifting the substrate intact from the reaction vessel; and peeling the fine particles or external additives for colorant off the substrate.

[0091] From the viewpoint of separability from fine particles or external additives for colorants, the substrate used in manufacturing the fine particles or external additives for colorants of the present invention is suitable as, for example, any of the following substrates: various flat plates made of metal, glass, ceramics, etc.; and resin particles. Among these, resin particles having a low degree of crosslinking and a certain degree of solubility are particularly preferred. The size of each resin particle is preferably 1 to 100 μm, because the particle size of the substrate is tens of times or more than that of the fine particles or external additives for colorants, thus it is easy to manufacture approximately hemispherical fine particles or external additives for colorants with generally flat surfaces and curved surfaces. Although the material of the resin particles is not particularly limited, polymethyl methacrylate (PMMA) particles and polystyrene fine particles manufactured by soap-free emulsion polymerization, etc., are suitable.

[0092] Furthermore, when dispersing organometallic compounds and substrates in a medium, known surfactants and known inorganic and organic dispersants can be used as dispersion stabilizers, respectively.

[0093] Examples of surfactants include:

[0094] (1) Anionic surfactants: alkyl sulfates, such as sodium lauryl sulfate; polyoxyethylene alkyl ether sulfates, such as sodium polyoxyethylene lauryl ether sulfate; sulfonates, such as sodium dodecylbenzene sulfonate and sodium alkylnaphthalene sulfonate; and higher fatty acid salts, such as sodium stearate and sodium laurylate;

[0095] (2) Cationic surfactants: quaternary ammonium salts, such as dodecylammonium bromide, dodecyltrimethylammonium bromide, dodecylpyridine chloride, dodecylpyridine bromide, hexadecyltrimethylammonium bromide, lauryltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride; and

[0096] (3) Nonionic surfactants: polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene derivatives, such as polyoxyethylene alkylene ethers; sorbitol fatty acid esters, such as sorbitol monolaurate and sorbitol monostearate; glycerol fatty acid esters, such as glycerol monostearate; and polyoxyethylene fatty acid esters, such as polyethylene glycol monolaurate.

[0097] In addition, examples of inorganic dispersants include: trivalent aluminum salts, such as aluminum chloride, aluminum sulfate, aluminum hydroxide, aluminum phosphate, and polyaluminum chloride; trivalent and divalent ferric salts, such as ferric chloride(III), ferric sulfate(III), ferric hydroxide(III), ferrous chloride(II), ferrous sulfate(II), ferrous hydroxide(II), polyferric sulfate, and polyferric silicate; divalent magnesium salts, such as magnesium chloride, magnesium sulfate, magnesium hydroxide, magnesium phosphate, and magnesium carbonate; divalent calcium salts, such as calcium chloride, calcium sulfate, tricalcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium hydroxide, hydroxyapatite, calcium carbonate, and calcium metasilicate; divalent cobalt salts, such as cobalt chloride and cobalt sulfate; divalent zinc salts, such as zinc phosphate; divalent barium salts, such as barium sulfate; silicate minerals, such as bentonite; and metal oxides, such as silicon dioxide and aluminum oxide.

[0098] In addition, examples of organic dispersants include polyvinyl alcohol, gelatin, methylcellulose, hydroxypropyl methylcellulose, ethylcellulose, sodium carboxymethylcellulose, and starch.

[0099] These dispersion stabilizers are selected appropriately based on the substrate material and their interaction with organometallic compounds. Furthermore, these dispersion stabilizers can be used alone or in combination.

[0100] Next, the components contained in the toner particles are described.

[0101] The toner particles in the toner of the present invention comprise binder resin, colorant and any other components.

[0102] As the binder resin, resins commonly used as binder resins for colorants (preferably non-crystalline resins) can be used. Specifically, styrene-acrylic resins (e.g., styrene-acrylate copolymers or styrene-methacrylate copolymers), polyester resins, epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, styrene-butadiene copolymers, or mixed or composite resins thereof can be used.

[0103] Examples of polymerizable monomers in styrene-acrylic resins may include the following vinyl polymerizable monomers: styrene; styrene derivatives, such as α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene; acrylic polymerizable monomers, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate, ethyl acrylate, diethyl phosphate Ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate; methacrylic polymerizable monomers, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters, such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, and vinyl formate; vinyl ethers, such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; and vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

[0104] In addition, polymerization initiators can be added during the polymerization of polymerizable monomers. Examples of polymerization initiators include: azo or diazo polymerization initiators, such as 2,2′-azobis-(2,4-dimethylpentanonitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis(cyclohexane-1-carboxynitrile), 2,2′-azobis-4-methoxy-2,4-dimethylpentanonitrile, and azobisisobutyronitrile; and peroxide polymerization initiators, such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl carbonate peroxide, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. Any such polymerization initiator is preferably added in an amount of 0.5 to 30.0 parts by weight relative to a total of 100 parts by weight of polymerizable monomers. These polymerization initiators can be used alone or in combination.

[0105] To control the molecular weight of the binder resin that forms the toner particles, a chain transfer agent can be added during the polymerization of the polymerizable monomers. The weight-average molecular weight of the binder resin is preferably from 5,000 to 100,000. The amount of chain transfer agent added is preferably from 0.001 to 15.000 parts by mass relative to 100 parts by mass of the total polymerizable monomers.

[0106] To control the molecular weight of the binder resin that forms the toner particles, a crosslinking agent can be added during the polymerization of the polymerizable monomer. Examples of crosslinking agents include divinylbenzene, bis(4-acryloyloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diacrylates of polyethylene glycol #200, #400 and #600, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester diacrylates, and compounds obtained by converting the above acrylates into methacrylates. As multifunctional crosslinking monomers, the following are provided: pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, low-polyester acrylates, and their methacrylates; 2,2-bis(4-methacryloyloxy-polyethoxyphenyl)propane; diallyl phthalate; triallyl cyanurate; triallyl isocyanurate; triallyl trimellitate; and diallyl chlorhexidine. The amount of crosslinking agent added is preferably from 0.001 to 15.000 parts by weight relative to 100 parts by weight of the total polymerizable monomers.

[0107] As a polyester resin, a polyester resin obtained by polycondensation of a carboxylic acid component and an alcohol component can be used.

[0108] Examples of carboxylic acid components include: dicarboxylic acids, such as oxalic acid, succinic acid, glutaric acid, maleic acid, adipic acid, β-methyl adipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citralic acid, diethylene glycol, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, p-heptanediic acid, octanoic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, and terephthalic acid. Acids, including isophthalic acid, o-phthalic acid, diphenylacetic acid, diphenyl-p,p′-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and cyclohexane dicarboxylic acid; and polycarboxylic acids such as trimellitic acid, pyromellitic acid, pyromellitic tetracarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid, itaconic acid, glutaric acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, and n-octenyl succinic acid. These components can be used alone or in combination.

[0109] Examples of alcohol components include: diols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosodecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4- Cyclohexanediol, 1,4-cyclohexanediol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanediol, polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, and epoxide adducts of the above bisphenols (e.g., ethylene oxide, propylene oxide, and butyl oxide); and polyols, such as glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolguanidine, tetraethylolguanidine, sorbitol, triphenol PA, phenolic varnish, cresol varnish, and epoxide adducts of the above ternary or higher polyphenols. These components can be used alone or in combination. Furthermore, the polyester resin can be a polyester resin containing urea groups.

[0110] There are no particular restrictions on the colorant, and the following known colorants may be used respectively.

[0111] Yellow iron oxides, naple yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, tartrate yellow lake, and other condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allyl amide compounds are used as yellow pigments. Specific examples include CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and 180.

[0112] As orange pigments, Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Benzidine Orange G, Indanisole Brilliant Orange RK, and Indanisole Brilliant Orange GK are given.

[0113] As red pigments, given are brownish-red iron oxides (colcothar), permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red C, lake red D, bright carmine 6B, bright carmine 3B, eosin lake, rhodamine lake B, alizarin lake, and other condensed azo compounds, diketylpyrrolopyrrole 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, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254.

[0114] As blue pigments, basic blue lakes are given, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue, fast sky blue, indanthrene BG, and other copper phthalocyanine compounds and their derivatives, 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.

[0115] As a purple pigment, fast violet B and methyl violet are given.

[0116] As green pigments, Pigment Green B, Malachite Green Lake, and Final Yellow Green G are given. As white pigments, Zinc White, Titanium Dioxide, Antimony White, and Zinc Sulfide are given.

[0117] As black pigments, carbon black, aniline black, non-magnetic ferrite, magnetite, and pigments tinted to black using yellow, red, and blue colorants are provided. These colorants can be used alone or as mixtures thereof, in a solid solution state.

[0118] The colorant content is preferably 3.0 to 15.0 parts by weight relative to 100 parts by weight of the total binder resin or polymeric monomers used to produce the binder resin.

[0119] The colorant may contain a release agent. There are no particular limitations on the release agent, and the following well-known release agents may be used: petroleum-based waxes such as paraffin, microcrystalline wax, and petrolatum, and their derivatives; lignite wax and its derivatives; hydrocarbon waxes produced by the Fischer-Tropsch process, and their derivatives; polyolefin waxes such as polyethylene and polypropylene, and their derivatives; natural waxes such as carnauba wax and candelilla wax, and their derivatives; higher fatty alcohols; fatty acids such as stearic acid and palmitic acid, or their compounds, amide waxes, ester waxes, or ketones; hydrogenated castor oil and its derivatives; plant-based waxes; animal-based waxes; and silicone resins. Derivatives include oxides, as well as block copolymers or graft-modified products with vinyl monomers. These release agents may be used alone or as mixtures thereof.

[0120] The content of the release agent is preferably 5.0 to 30.0 parts by weight relative to 100 parts by weight of the total adhesive resin or polymeric monomers used to produce the adhesive resin.

[0121] The colorant may contain a crystalline resin. There are no particular limitations on the crystalline resin, and known resins may be used. Specific examples include crystalline polyester resins and crystalline acrylic resins. The crystalline resin may be a block polymer having crystalline and non-crystalline sites.

[0122] The toner may include a charge control agent, and known charge control agents may be used. The amount of such charge control agent added is preferably 0.01 to 10.00 parts by weight relative to a total of 100 parts by weight of the adhesive resin or the polymerizable monomers used to produce the adhesive resin.

[0123] In addition to the fine particles of the present invention, various organic or inorganic fine powders can be added to the outside of the colorant particles as needed.

[0124] For example, the following fine powders are used as organic or inorganic fine powders.

[0125] (1) Flowability enhancers: silica, alumina, titanium dioxide, carbon black and fluorocarbon.

[0126] (2) Abrasives: metal oxides (e.g., strontium titanate, cerium oxide, aluminum oxide, magnesium oxide and chromium oxide), nitrides (e.g., silicon nitride), carbides (e.g., silicon carbide), and metal salts (e.g., calcium sulfate, barium sulfate and calcium carbonate).

[0127] (3) Lubricants: fluorinated resin powders (e.g., vinylidene fluoride and polytetrafluoroethylene) and fatty acid metal salts (e.g., zinc stearate and calcium stearate).

[0128] (4) Charge-controlled particles: metal oxides (e.g., tin oxide, titanium oxide, zinc oxide, silicon dioxide and aluminum oxide) and carbon black.

[0129] To improve the flowability of toners and homogenize the charge of toner particles, the surface of fine organic or inorganic powders can be hydrophobically treated. Examples of treatment agents used for hydrophobic treatment of fine organic or inorganic powders include unmodified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents can be used alone or in combination.

[0130] In addition, examples of methods for manufacturing toner particles are listed below.

[0131] (1) Suspension polymerization method: The colorant particles are obtained by granulating a polymeric monomer composition containing a polymeric monomer capable of generating a binder resin, a release agent, and a colorant as needed in an aqueous medium to polymerize the polymeric monomer.

[0132] (2) Crushing method: Colorant particles are obtained by melting and mixing binder resin, mold release agent, and colorant as needed, and crushing the result.

[0133] (3) Dissolution and suspension method: The colorant particles are obtained by dissolving the binder resin and release agent, as well as the colorant as needed, in an organic solvent to prepare an organic phase dispersion; suspending the liquid in an aqueous medium; granulating and polymerizing the suspension; and then removing the organic solvent.

[0134] (4) Emulsion polymerization method: Toner particles are obtained by aggregating binder resin particles, release agent particles, and colorant particles as needed in an aqueous medium; and the aggregates are associated.

[0135] Examples of aqueous media include water; and mixed solvents of water and alcohols such as methanol, ethanol or propanol.

[0136] Various measurement methods related to this invention are described below.

[0137] <Methods for confirming that fine particles or external additives used in colorants are solid>

[0138] The fact that fine particles or toners are solid external additives was confirmed using scanning transmission electron microscopy (STEM).

[0139] Samples for STEM observation are prepared as described below.

[0140] First, the toner, or fine particles, or toner with external additives is spread on a coverslip (Matsunami Glass Ind., Ltd., square coverslip; SQUARE No.1) to form a layer, and then an Os film (5nm) and a naphthalene film (20nm) are applied as protective films to the toner, or fine particles, or toner with external additives using an osmium plasma coating machine (Filgen, Inc., OPC80T).

[0141] Next, the PTFE tube was filled with light-curing resin D800 (JEOL Ltd.). The coverslip is then placed quietly on the tube in a direction that allows the toner, fine particles, or toner additives to contact the light-curing resin D800. In this state, light is applied to cure the resin, and then the coverslip and tube are removed. This results in a cylindrical resin structure with the toner, fine particles, or toner additives embedded on its outermost surface.

[0142] Using an ultrasonic microtome (Leica Microsystems, UC7), the cutting begins at a speed of 0.6 mm / s from the outermost surface of the cylindrical resin to expose a cross-section of the central portion of the fine particles or toner external additive. The exposed cross-section is then cut to a thickness of 100 nm. This produces a thin-film sample of the cross-section of the fine particles or toner external additive. The cross-section of the central portion of the fine particles or toner external additive can be obtained using this method.

[0143] The STEM equipment used, as well as the observation methods and conditions, are described below.

[0144] Equipment: Tecnai TF20XT transmission electron microscope manufactured by FEI Corporation

[0145] Images of thin-section samples were obtained by setting the STEM probe size to 1 nm and the image size to 1,024 × 1,024 pixels, respectively. Furthermore, images were obtained by adjusting the contrast and brightness of the STEM detector control panel (used for bright-field imaging) to 1,425 and 3,750, respectively, and adjusting the contrast, brightness, and gamma of its image control panel to 0.0, 0.5, and 1.00, respectively. Observations were performed at magnifications ranging from 100,000 to 200,000.

[0146] When the fine particles or toner additives are observed to be filled with solid material and therefore not hollow in the obtained STEM image, the fine particles or additives are judged to be solid. Furthermore, in this invention, even when the fine particles or additives are solid, fine particles or toner additives with a df / h ratio greater than 0.10 are considered hollow. For example, Figure 2A , Figure 2B or Figure 2D The fine particles or toners shown are solid with external additives, while Figure 2C The fine particles or toners shown are hollow with external additives.

[0147] <Method for confirming that fine particles or external additives used in colorants are approximately hemispherical>

[0148] The fact that fine particles or toners are external additives in a roughly hemispherical shape was confirmed by scanning transmission electron microscopy (STEM).

[0149] The sample preparation, STEM equipment, and methods and conditions for STEM observation are described above.

[0150] The average number of fine particles or toners using external additives with ratios df / h, l1 / l2, and s1 / s2 was calculated from the obtained STEM image using the image processing software ImageJ (developer: Wayne Rasband). See below for reference. Figures 2A to 2D Describe the calculation method.

[0151] First, use the Straight Line tool in the software's toolbar to select the scale bar in the observation conditions display area shown at the bottom of the image. In this state, select Set Scale from the Analyze menu. A new window will open. Enter the pixel distance of the selected line in the "Distance in Pixels" field. Enter the scale value (e.g., 100) in the "Known Distance" field and the scale unit (e.g., nm) in the "Unit of Measurement" field. Then click the OK button. The scale setting is now complete.

[0152] Next, select ROI Manager from the Tools menu, and check the "Show All" and "Labels" checkboxes in the newly opened ROI Manager window. Then, use the Straight Line tool in the toolbar to draw... Figures 2A to 2D Each of the lines shown is an imaginary straight line Li connecting the line Lf originating from a generally flat surface of fine-grained or toner-based external additives to the two intersection points Pa and Pb of the line Lc originating from its curved surface. In this state, select Add in the ROI Manager window. Next, draw a straight line orthogonal to the imaginary straight line Li and select Add, where the distance between the two points becomes the maximum length "df", one of which is the intersection of the imaginary straight line Li and this straight line, and the other of which is the intersection of the line Lf originating from a generally flat surface of fine-grained or toner-based external additives and this straight line. In addition, draw a line Ls1 orthogonal to the imaginary line Li, and select Add. The maximum height "h" is determined by either the distance Da between point Pc and point Pe, or the distance Db between point Pd and point Pe. Point Pc is the intersection of the imaginary line Li and line Ls1. Point Pe is the intersection of line Lc (originating from a curved surface) and line Ls1. Point Pd is the intersection of line Lf (originating from a roughly flat surface) and line Ls1. Then, perform analysis when the ROI Manager window's Measure option is selected. Obtain the lengths corresponding to the maximum length df and the maximum height "h" from the newly opened Results window, and calculate the ratio df / h.

[0153] In addition, use the elliptical tool (Elliptical selections) in the toolbar to draw. Figure 2E and Figure 2FEach of the ellipses e1 and e2 shown in the diagram, ellipse e1 passes through two intersection points of the generally flat surface and the curved surface of the fine-grained or toner-based external additive, and is externally inscribed in the curved surface of the fine-grained or toner-based external additive. Ellipse e2 passes through two intersection points of the generally flat surface and the curved surface of the fine-grained or toner-based external additive, and is internally inscribed in the curved surface of the fine-grained or toner-based external additive. In this state, select Add in the ROI Manager window. Subsequently, as... Figure 2E 'and Figure 2F As shown in each of the diagrams, use the Straight Line tool in the toolbar to draw a straight line that serves as the major axis l1 and minor axis s1 of ellipse e1, and the major axis l2 and minor axis s2 of ellipse e2, and select Add. Next, perform the analysis when the Measure option is selected in the ROI Manager window. Obtain the lengths corresponding to the major axis l1 of ellipse e1, the major axis l2 of ellipse e2, the minor axis s1 of ellipse e1, and the minor axis s2 of ellipse e2 from the newly opened Results window, and calculate the ratios l1 / l2 and s1 / s2.

[0154] The above steps were performed on 100 fine particles to be evaluated or 100 particles of toner with external additives to be evaluated, and the average number of ratios df / h, l1 / l2, and s1 / s2 was calculated.

[0155] Fine particles or toners that can be confirmed by the above method to meet the following two conditions are judged to be approximately hemispherical by external additives: (1) the average number of particles with a ratio of df / h is 0.00 to 0.10; and (2) the average number of particles with a ratio of l1 / l2 is 0.90 to 1.10, and the average number of particles with a ratio of s1 / s2 is 0.90 to 1.10.

[0156] <Method for calculating the average number of longest diameter "w" values ​​on a roughly flat surface of fine particles or external additives for colorants>

[0157] The average number of longest diameters "w" on the generally flat surface of fine particles or external additives for toners was calculated using scanning electron microscopy (SEM).

[0158] The SEM equipment, observation methods, and conditions are described below.

[0159] Equipment: S-4800 ultra-high resolution field emission scanning electron microscope (hereinafter referred to as "S-4800") manufactured by Hitachi High-Technologies Corporation.

[0160] (1) Sample production

[0161] A thin layer of conductive paste (product number: 16053, manufactured by TED PELLA, Inc., PELCO colloidal graphite, isopropanol-based) is applied to the sample stage (aluminum sample stage, size 15mm × 6mm), and toner, or fine particles, or toner additives are sprayed onto it. Excess fine particles or excess toner additives are then removed from the sample stage by blowing air, and platinum is then vaporized onto the residue at 15mA for 15 seconds. The sample stage is placed in the sample holder, and its height is adjusted to 30mm using a sample height gauge.

[0162] (2) Setting observation conditions using S-4800

[0163] Inject liquid nitrogen into the anti-fouling trap mounted on the S-4800's housing until the liquid nitrogen flows out, then let it stand for 30 minutes. Start the S-4800's "PC-SEM" to perform flushing (cleaning the FE chip as the electron source). Click the acceleration voltage display on the S-4800's control panel and press the [Flushing] button to open the flushing performance dialog box. Confirm that the flushing intensity is 2 and proceed with flushing. Confirm that the emission current induced by flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800's housing. Press the [Origin] button on the control panel to move the sample holder to the observation position.

[0164] Click the accelerating voltage display to open the HV setting dialog box, and set the accelerating voltage and emission current to [2.0kV] and [10μA], respectively. In the [Basics] tab of the S-4800's operation panel, set the signal selection mode to [SE], and select [Low] to put the SE detector into the mode for observing reflected electron images. Also in the [Basics] tab of the operation panel, set the probe current of the electron optics system condition block to [Normal], its focus mode to [UHR], and its WD to [8.0mm]. Press the [ON] button on the accelerating voltage display of the control panel to apply the accelerating voltage to the sample.

[0165] (3) Focus adjustment

[0166] Drag the area in the magnification display section of the control panel to set the magnification to 5,000 (5k). Rotate the focus knob [COARSE] on the operation panel, and adjust the aperture alignment when the sample is focused to a certain extent. Click [Align] on the control panel to display the alignment dialog box, and select [Beam]. Rotate the STIGMA / ALIGNMENT knob (X,Y) on the operation panel to move the desired beam to the center of the concentric circles.

[0167] Next, select [Aperture] and rotate the STIGMA / ALIGNMENT knobs (X,Y) one by one to stop the movement of the sample image or to align the beam with the center to minimize movement. Close the aperture dialog box and focus the sample using autofocus. Repeat this operation twice more to focus the sample. With the midpoint of the observed particle's maximum diameter aligned with the center of the S-4800's measurement screen, drag the magnification display area on the control panel to set the magnification to 10,000 (10k). Rotate the focus knob [COARSE] on the operation panel, and adjust the aperture alignment when the sample is focused to a certain extent. Click [Align] on the control panel to display the alignment dialog box and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X,Y) on the operation panel to move the beam to be displayed to the center of the concentric circles.

[0168] Next, select [Aperture] and rotate the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the image movement or to align the beam with the center to minimize movement. Close the Aperture dialog box and focus the sample using autofocus. Then, set the magnification to 50,000 (50k) and adjust the focus using the focus knob and STIGMA / ALIGNMENT knob in the same way as above, then focus the sample again using autofocus. Repeat this process to focus the sample.

[0169] (4) Image saving

[0170] Brightness was adjusted using the ABC mode, and the size and magnification were set to 640×480 pixels and 10,000 to 50,000 (10 to 50k), respectively. Images of the fine particles or external additives for toners on the surface of each toner particle, or images of the fine particles or external additives for toners on the sample stage surface, were obtained from above (in the direction from which their generally flat surfaces can be observed in the projected image of the fine particles or external additives for toners) and saved.

[0171] The average number of longest diameters "w" of the generally flat surface of the fine particles or toner external additives was calculated from the obtained SEM image using the image processing software ImageJ (developer: Wayne Rasband). The scale was set as described above, and the average number of longest diameters "w" of the generally flat surface of the fine particles or toner external additives was calculated using the following procedure.

[0172] Select "Set Measurements" from the software's Analysis menu, and check the "Feret's diameter" checkbox. Additionally, select "ROI Manager" from the Tools menu within the Analysis menu, and check the "Show All" and "Labels" checkboxes in the newly opened ROI Manager window. Then, as follows... Figure 3 As shown, use the Elliptical Tool (Elliptical selections) in the software toolbar to approximate the roughly flat surface of a fine particle or a particle with an external toner additive as an ellipse. In this state, select Add in the ROI Manager window. Similarly, approximate the roughly flat surface of a fine particle or an external toner additive that is different from the selected fine particle or external toner additive as an ellipse, and select Add. After repeating this operation for all fine particles or external toner additive particles in the image, perform the analysis when Measure is selected in the ROI Manager window. Obtain the longest diameter "w" (Ferret diameter) of the roughly flat surface of each fine particle or external toner additive particle from the newly opened Results window. The longest diameter w of the roughly flat surface of the fine particle or external toner additive obtained thus is the distance between the longest straight lines connecting any two points on the outer periphery of the roughly flat surface of the fine particle or external toner additive.

[0173] The above process was performed on 100 fine particles to be evaluated, and the average number of longest diameters "w" of the generally flat surfaces of the fine particles or external additives for colorants was calculated.

[0174] <Method for confirming the presence or absence of fine particles on the surface of toner granules and a generally flat surface>

[0175] Use scanning electron microscopy (SEM) to confirm whether a generally flat surface of fine particles is observed on the surface of the toner particles.

[0176] In addition to obtaining images by observing the surface of each toner particle from any direction, the SEM equipment, observation methods, and conditions are as described above.

[0177] From the obtained SEM images, the percentage of fine particles with angles greater than 90° and less than 270° on the surface of the toner particles was calculated when the angle of each fine particle in contact with the surface of the toner particles was defined as 0°. 200 fine particles were counted on the surface of the toner particles. Examples of the angles of the fine particles when viewed laterally are shown in [examples]. Figure 4 middle.

[0178] When it is confirmed by the above method that fine particles with an angle greater than 90° and less than 270° account for more than 1.0% of the fine particles present on the surface of the toner particles, it is determined that a generally flat surface of fine particles is observed on the surface of the toner particles.

[0179] <Method for calculating the average number of values ​​for the ratio h / b of the maximum height "h" to the maximum width "b">

[0180] The average number of ratios h / b defined as follows is calculated using scanning transmission electron microscopy (STEM) when observing the cross-section of fine particles or external additives for toners: the maximum height "h" is defined as the distance between the intersection of the line connecting the two intersections of the generally flat surface and the curved surface with the line or the intersection of the curved surface and the line, or the distance between the intersection of the generally flat surface and the line and the intersection of the curved surface and the line, which is orthogonal to the line connecting the two intersections of the generally flat surface and the line, which is orthogonal to the intersection of the curved surface and the line, which is orthogonal to the intersection of the generally flat surface and the line, which is orthogonal to the intersection of the curved surface and the line, which is orthogonal to the intersection of the two intersections of the generally flat surface and the line, which is orthogonal to the intersection of the two intersections of the curved surface and the line, which is orthogonal to the intersection of the two intersections of the generally flat surface and the line, which is orthogonal to the intersection of the two intersections of the curved surface and the line, which is orthogonal to the intersection of the two intersections of the generally flat surface and the line, which is orthogonal to the intersection of the two intersections of the curved surface and the line, which is orthogonal to the intersection of the two intersections of the two ...

[0181] The sample preparation, STEM equipment, and observation methods and conditions for STEM observation are as described above.

[0182] The average h / b ratio of fine particles or toners with external additives was calculated from the obtained STEM image using the image processing software ImageJ (developer: Wayne Rasband). The scale was set as described above, and the subsequent procedures are as follows.

[0183] From the software's Analysis menu, select ROI Manager from Tools, and in the newly opened ROI Manager window, check the "Show All" and "Labels" checkboxes. Then, similarly, draw the line Ls1 representing the maximum height "h". In this state, select Add in the ROI Manager window. Next, as described above... Figures 2A to 2DIn each example, draw a line Ls2 parallel to the imaginary line Li and orthogonal to the line Ls1 representing the maximum height "h". The distance Dc between the two intersection points Pf and Pg of line Ls2 and line Lc becomes the maximum width "b", and select Add. Then, perform the analysis when the Measure option is selected in the ROI Manager window. Obtain the lengths corresponding to the maximum height "h" and maximum width "b" from the newly opened results window, and calculate the ratio h / b.

[0184] The above process was performed on 100 fine particles to be evaluated or 100 particles of toner with external additives to be evaluated, and the average number of h / b ratios was calculated.

[0185] <Method for confirming the structure represented by equations (D), (T), and (Q)>

[0186] The fact that the external additives for fine particles or toners of the present invention include at least one structure represented by formula (D), formula (T) and formula (Q) was confirmed by nuclear magnetic resonance (NMR) equipment.

[0187] In the case of fine particles or external additives used as toners, the fine particles or external additives are used as samples for NMR measurements. In the case of toners, the sample is prepared, for example, by separating the fine particles as described below.

[0188] 160g of sucrose (manufactured by Kishida Chemical Co., Ltd.) was dissolved in 100mL of ion-exchange water while being heated in a water bath. This prepared a sucrose concentrate. 31g of the sucrose concentrate and 6mL of Contaminon N (a 10% by mass aqueous solution of a neutral detergent for precision measuring device cleaning, pH 7, composed of nonionic surfactants, anionic surfactants, and organic detergent builders, manufactured by Wako Pure Chemical Industries, Ltd.) were added to a centrifuge tube (capacity: 50ml). 1.0g of toner was added to the mixture, and the toner clumps were broken up using a spatula or similar tool. The centrifuge tube was shaken for 20 minutes at 300 strokes per minute (spm) using a shaker (product name: AS-1N, sold by As One Corporation). After shaking, the solution was transferred to a glass tube (50 mL) for oscillating rotor and centrifuged using a centrifuge (trade name: H-9R, manufactured by Kokusan Co., Ltd.) at 3,500 rpm for 30 minutes.

[0189] This operation separates the toner particles and fine particles from each other. Visually confirm that the toner and aqueous solution are sufficiently separated, and remove the toner that has separated to the top layer. Centrifuge the aqueous solution, and separate the fine particles for collection. Dry the resulting material in a dryer for at least 1 hour. Thus, a measurement sample is obtained. Repeat this operation multiple times to ensure the required quantity.

[0190] In the structures represented by equations (D), (T), and (Q), Ra, Rb, and Rc, bonded to silicon atoms, are... 13 Confirmation was made using C-NMR (solid-state) measurements. The measurement conditions are as follows.

[0191] “ 13 C-NMR (Solid State) Measurement Conditions

[0192] Equipment: JNM-ECX 500II manufactured by JEOL Resonance Inc.

[0193] Sample tubes:

[0194] Sample: 150mg fine particles or colorant with external additives

[0195] Temperature measured: room temperature

[0196] Pulse mode: CP / MAS

[0197] Measured nuclear frequency: 123.25MHz 13 C)

[0198] Reference material: adamantane (external standard: 29.5 ppm)

[0199] Sample speed: 20 kHz

[0200] Contact time: 2ms

[0201] Delay time: 2s

[0202] Number of scans: 1,024

[0203] In the structures represented by formulas (D), (T), and (Q), the presence of Ra, Rb, and Rc is confirmed by the presence or absence of signals generated by, for example, the following organic groups: alkyl groups, such as methyl (Si-CH3), ethyl (Si-C2H5), propyl (Si-C3H7), butyl (Si-C4H9), pentyl (Si-C5H9), etc. 11 ), hexyl (Si-C6H) 13 ), heptyl (Si-C7H) 15 ) or octyl (Si-C8H) 17); aryl, such as phenyl (Si-C6H5-); alkylene, such as methine (>CH-Si), methylene (Si-CH2-), ethylene (Si-C2H4-) or trimethylene (Si-C3H6-); and arylene, such as phenylene (Si-C6H4-), each bonded to a silicon atom.

[0204] In the structures represented by formulas (D), (T), and (Q), the siloxane bond portion is... 29 This was confirmed by Si-NMR (solid-state) measurements. The measurement conditions are as follows.

[0205] “ 29 Si-NMR (Solid State) Measurement Conditions

[0206] Equipment: JNM-ECX 500II manufactured by JEOL Resonance Inc.

[0207] Sample tubes:

[0208] Sample: 150mg fine particles or colorant with external additives

[0209] Temperature measured: room temperature

[0210] Pulse mode: CP / MAS

[0211] Measured nuclear frequency: 97.38MHz 29 Si)

[0212] Reference material: DSS (external standard: 1.534 ppm)

[0213] Sample speed: 10 kHz

[0214] Contact time: 10ms

[0215] Delay time: 2s

[0216] Number of scans: 2,000 to 8,000

[0217] After measurement, the peaks of various silane components with different substituents and different bonding groups in the external additives of fine particles or toners were separated into X1, X2, X3 and X4 structures by curve fitting, and the area of ​​each peak was calculated.

[0218] The X1 structure represented by equation (1) is: (Rd)(Re)(Rf)SiO 1 / 2

[0219] The X2 structure represented by equation (2): (Rg)(Rh)Si(O) 1 / 2 )2

[0220] The X3 structure represented by equation (3): RiSi(O 1 / 2 )3

[0221] The X4 structure represented by equation (4): Si(O) 1 / 2 )4

[0222]

[0223] In formulas (1) to (4), Rd, Re, Rf, Rg, Rh and Ri each represent an organic group, halogen atom, hydroxyl group, acetoxy group or alkoxy group bonded to silicon atoms.

[0224] In equations (1) to (4), the structures of the parts enclosed by the quadrilaterals are X1 structure to X4 structure, respectively.

[0225] External additives are used, either through fine particles or colorants. 29 In the Si-NMR measurements, the ratio of the peak area of ​​the X2 to X4 structures belonging to the structures represented by formulas (D), (T) and (Q) to the total peak area of ​​the organosilicon polymer is preferably 50 mol% or more, more preferably 70 mol% or more.

[0226] When a more detailed confirmation of the structure represented by equations (D), (T), and (Q) is required, it can be achieved by using... 1 The H-NMR measurement results combined with 13 C-NMR measurement results and 29 The determination was made using Si-NMR measurements.

[0227] According to the present invention, toners, external additives for toners, and fine particles that provide excellent low-temperature fixing properties and maintain their initial cleanliness even after continuous mechanical stress can be provided.

[0228] Example

[0229] The invention is described in more detail below with the aid of specific production examples, embodiments, and comparative examples. However, the invention is by no means limited thereto. Unless otherwise stated, the term "parts" in the following formulations refers to "parts by weight".

[0230] [Production example of roughly hemispherical fine particles 1]

[0231] <Preparation steps of precursor aqueous solution 1>

[0232] 60.0 parts of ion-exchanged water were weighed into a reaction vessel including a stirrer and a thermometer, and its pH was adjusted to 3.0 with 10% hydrochloric acid by mass. While stirring the product, it was heated to a temperature of 60°C. Then, 40.0 parts of methyltrimethoxysilane were added to the heated product, and the mixture was stirred for 2 hours. The oil and water layers were visually observed to have mixed into a single layer without separation. The mixture was then cooled to provide precursor aqueous solution 1.

[0233] <Aggregation Steps>

[0234] 1,000.0 parts of ion-exchanged water were weighed into a reaction vessel including a stirrer and a thermometer, and 6.0 parts of NOIGEN EA177 (manufactured by DKS Co., Ltd.) and 380.0 parts of PMMA particles (non-crosslinked, number average particle size: 10 μm) were added. While stirring the mixture at 180 rpm, the mixture was heated to 50 °C and held at this temperature for 30 minutes. While continuing stirring, 34.0 parts of precursor aqueous solution 1 were added to the mixture. The result was kept undisturbed for 30 minutes, and then the pH was adjusted to 9.0 with an aqueous solution of sodium hydroxide. The result was further kept undisturbed for 300 minutes to form generally hemispherical fine particles, each free of silicone polymer, on the surface of the PMMA particles.

[0235] <Washing Steps>

[0236] After the polymerization step is completed, the reaction solution is cooled and subjected to solid-liquid separation using a pressure filter to provide a filter cake of PMMA particles. The filter cake is then slurried again with deionized water to provide a dispersion again, and the dispersion is then subjected to solid-liquid separation again using a filter. This process of slurrying and solid-liquid separation is repeated several times, and finally, the result is subjected to solid-liquid separation to obtain a filter cake of PMMA particles.

[0237] <Separation and Drying Steps>

[0238] After the washing step, the filter cake of PMMA particles was added to 1,000.0 parts of acetone in a reaction vessel including a stirrer, and the mixture was kept for 1 hour while stirring at 180 rpm. The complete dissolution of the PMMA particles was visually observed, and the mixture was then centrifuged at 15,000 rpm for 10 minutes. The precipitate was recovered and vacuum dried. The dried product was then pulverized as needed using a pulverizer (manufactured by Hosokawa Micron Corporation), and the approximately hemispherical fine particles were separated using an air classifier. Thus, approximately hemispherical fine particles 1 were obtained. The physical properties of the obtained approximately hemispherical fine particles 1 are shown in Table 2.

[0239] [Production examples of approximately hemispherical fine particles 2 to 20, and comparative examples of approximately hemispherical fine particles 1 and 2]

[0240] Except for the formulation and production conditions shown in Table 1, approximately hemispherical fine particles 2 to 20 were obtained in the same manner as in the production example of approximately hemispherical fine particles 1, and approximately hemispherical fine particles 1 and 2 were compared. The physical properties of the obtained fine particles are shown in Table 2.

[0241]

[0242]

[0243] In Table 2, the symbol "○" in the "Solid" column indicates that the fine particles are solid, and the symbol "×" indicates that the fine particles are hollow. In addition, the symbol "○" in the "Approximately Hemispherical" column indicates that the fine particles are approximately hemispherical, and the symbol "×" indicates that the fine particles are not approximately hemispherical.

[0244] [Example of hollow fine particle production]

[0245] 500g of ion-exchanged water was added to a reaction vessel, and 0.45g of a 48% sodium hydroxide aqueous solution was added to provide an aqueous solution. 65g of methyltrimethoxysilane and 50g of tetraethoxysilane were added to this aqueous solution, and the hydrolysis reaction was carried out by stirring the mixture for 1 hour while maintaining the temperature at 13-15°C. Furthermore, 0.31g of a 15% α-(p-nonylphenyl)-ω-hydroxy (polyoxyethylene) aqueous solution was added to the hydrolysis product, and the hydrolysis reaction was carried out by stirring the mixture at this temperature for 3 hours. A transparent reaction product containing silanol compounds was thus obtained. Next, while maintaining the pH of the resulting reaction product, the temperature was maintained at 70°C, and a condensation reaction was carried out by stirring the product for 5 hours. An aqueous suspension containing hollow fine particles formed from individual organosilicon compounds was thus obtained. The aqueous suspension was filtered through a membrane filter, and the liquid portion passing through the filter was centrifuged to separate the white fine particles. The separated white fine particles were washed with water and dried with hot air at 150°C for 5 hours to obtain hollow fine particles. The physical properties of the obtained hollow fine particles are shown in Table 2.

[0246] [Example of production of spherical sol-gel silica fine particles]

[0247] 500.0 g of methanol, 36.0 g of water, and 41.0 g of 28% (w / w) ammonia solution were added to a glass reactor equipped with a stirrer, dropping funnel, and thermometer, and mixed. The temperature of the resulting solution was adjusted to 35°C, and while stirring the solution, 932.0 g of tetramethoxysilane and 335.0 g of 5.5% (w / w) ammonia solution were simultaneously added. Tetramethoxysilane was added dropwise over 6 hours, followed by ammonia addition over 5 hours. After the addition of tetramethoxysilane was completed, hydrolysis was carried out by further stirring for 0.5 hours. This yielded a dispersion of hydrophilic spherical sol-gel silica particles in methanol and water. An ester adapter and cooling tube were then installed on the glass reactor, and the dispersion was thoroughly dried under reduced pressure at 80°C. The resulting silica particles were heated in a thermostat at 400°C for 10 minutes.

[0248] The resulting fine silica particles were pulverized using a pulverizer (manufactured by Hosokawa Micron Corporation).

[0249] Next, 500g of fine silica particles were added to a 1000ml PTFE-lined stainless steel autoclave. The interior of the autoclave was purged with nitrogen, and then the agitator blades installed in the autoclave were moved at a speed of 6.6s. -1 While rotating at (revolutions), 0.5 g of hexamethyldisilazane (HMDS) and 0.1 g of water were uniformly sprayed onto the silica powder in a mist manner using a two-fluid nozzle. After stirring the powder for 30 minutes, the autoclave was sealed and heated at 220°C for 2 hours. Subsequently, while heating, the pressure of the system was reduced, and ammonia removal was performed. This yielded spherical sol-gel silica fine particles. The physical properties of the obtained spherical sol-gel silica fine particles are shown in Table 2.

[0250] [Example of production of fine silica particles via fumed silica process]

[0251] Make the specific surface area of ​​BET 30m² 2 Commercially available fine silica particles were passed at a rate of 0.5 kg / hr through an atmosphere created by a burner at a temperature of 1,800 °C, and collected by blowing the silica particles into a collection line and filter using a blower. The collected particles were then surface-treated with 8 parts by mass of hexamethyldisilazane and classified using an air classifier. This yielded fumed silica fine particles. The physical properties of the obtained fine particles are shown in Table 2.

[0252] [Production example of colorant granules 1]

[0253] <Preparation steps of aqueous media>

[0254] 14.0 parts of sodium phosphate (manufactured by Rasa Industries, Ltd., dodecahydrate) were added to 1,000.0 parts of ion-exchange water in a reaction vessel, and the mixture was kept at 65°C for 1 hour while purging the vessel with nitrogen. While stirring the mixture at 12,000 rpm using a TKHOMO MIXER (manufactured by Tokushu Kika Kogyo Co., Ltd.), an aqueous solution of calcium chloride (obtained by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchange water) was added to the mixture in one step to prepare an aqueous medium containing a dispersant stabilizer. Furthermore, 10% by mass of hydrochloric acid was added to the aqueous medium to adjust its pH to 6.0. Thus, the aqueous medium was obtained.

[0255] <Preparation steps of polymeric monomer compositions>

[0256] • Styrene: 60.0 parts

[0257] • CI Pigment Blue 15:3: 6.5 parts

[0258] The above materials were fed into a grinding mill (manufactured by Mitsui Miike Chemical Engineering Machinery, Co., Ltd.) and dispersed at 220 rpm for 5 hours using zirconium oxide particles, each with a diameter of 1.7 mm, to prepare a pigment dispersion. The following materials were then added to the pigment dispersion.

[0259]

[0260] (The polycondensation product of propylene oxide-modified bisphenol A (2 mol adduct) and terephthalic acid (molar ratio: 10:12), glass transition temperature Tg = 68℃, weight-average molecular weight Mw = 10,000, molecular weight distribution Mw / Mn = 5.12)

[0261] • Fischer-Tropsch wax (melting point: 78℃): 10.0 parts

[0262] • Charge control agent: 0.5 parts

[0263] (Aluminum compounds of 3,5-di-tert-butylsalicylic acid)

[0264] The temperature of the mixture was maintained at 65°C, and the material was uniformly dissolved and dispersed in the pigment dispersion at 500 rpm using a TKHOMO MIXER (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare a polymerizable monomer composition.

[0265] <Granulation Steps>

[0266] While maintaining the temperature of the aqueous medium and the speed of the agitator at 70°C and 12,000 rpm, respectively, the polymerizable monomer composition was added to the aqueous medium, and 9.0 parts of tert-butyl peroxypentanoate as a polymerization initiator were added to the mixture. The mixture was granulated for 10 minutes while maintaining the speed of the agitator at 12,000 rpm.

[0267] <Aggregation Steps>

[0268] The mixer was replaced with a propeller-type mixer, and polymerization was carried out for 5 hours while the granulated product was stirred at 150 rpm and kept at 70°C. The temperature was then increased to 95°C, and the product was heated at this temperature for 5 hours to allow the polymerization reaction to proceed. This yielded a slurry of colorant granules.

[0269] <Washing and Drying Steps>

[0270] After the polymerization step, the slurry of toner particles was cooled, and hydrochloric acid was added to the slurry to adjust the pH of the system to below 1.5, followed by stirring for 1 hour. Then, the mixture was subjected to solid-liquid separation using a pressure filter to provide a toner filter cake. The toner filter cake was then slurried again with deionized water to provide a dispersion again, and the dispersion was then subjected to solid-liquid separation again using a pressure filter. This process of slurrying and solid-liquid separation was repeated until the conductivity of the filtrate became below 5.0 μS / cm. Finally, the resulting product was subjected to solid-liquid separation to provide a toner filter cake.

[0271] The obtained toner filter cake was dried using a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and fine and coarse powders were removed using a multi-stage classifier utilizing the wall adhesion effect. This yielded toner particles 1. Drying was carried out at an inlet temperature of 90°C and a dryer outlet temperature of 40°C, and the feed rate of the toner filter cake was adjusted according to its moisture content to ensure the outlet temperature did not deviate from 40°C. The resulting toner particles 1 had a weight-average particle size of 6.2 μm.

[0272] [Production example of colorant granules 2]

[0273] <Preparation steps of polyester resin 1>

[0274] • Terephthalic acid: 11.1 mol

[0275] • Bisphenol A adduct with 2 mol propylene oxide (PO-BPA): 10.9 mol

[0276] The monomers and esterification catalyst were added together into an autoclave equipped with a pressure reducing device, a water separation device, a nitrogen introduction device, a temperature measuring device, and a stirring device. Under a nitrogen atmosphere, while reducing the pressure inside the autoclave, the mixture was reacted at 215°C using conventional methods until a Tg of 70°C was obtained. Polyester resin 1 was thus obtained. The weight-average molecular weight (Mw) of the obtained polyester resin 1 was 7,930, and the number-average molecular weight (Mn) was 3,090.

[0277] <Preparation steps of polyester resin 2>

[0278] • Bisphenol A ethylene oxide 2 mol adduct: 725 parts by weight

[0279] Phthalic acid: 285 parts by weight

[0280] • Dibutyltin oxide: 2.5 parts by weight

[0281] The above materials were reacted with each other for 7 hours by stirring at 220°C. Furthermore, the result was reacted under reduced pressure for 5 hours. The result was then cooled to 80°C and added to a solution of 190 parts by mass of isophorone diisocyanate in ethyl acetate. The mixture was then reacted for 2 hours to provide an isocyanate-containing polyester resin. Using a portion of the resulting reaction solution as is, 25 parts by mass of the isocyanate-containing polyester resin and 1 part by mass of isophorone diamine were reacted with each other at 50°C for 2 hours. Thus, polyester resin 2, with a polyester containing urea groups as the main component, was obtained. The obtained polyester resin 2 had a weight-average molecular weight (Mw) of 22,990, a number-average molecular weight (Mn) of 3,020, and a peak molecular weight of 6,810.

[0282] <Preparation steps of toner granules>

[0283] 700 parts by mass of ion-exchanged water, 1,000 parts by mass of 0.1 mol / L Na3PO4 aqueous solution, and 24.0 parts by mass of 1.0 mol / L HCl aqueous solution were added to a five-necked pressure vessel including a reflux pipe, a stirrer, a thermometer, and a nitrogen inlet pipe. The mixture was stirred at 12,000 rpm using a TKHOMO MIXER (manufactured by Tokushu Kika Kogyo Co., Ltd.) while maintaining the temperature of the mixture at 63°C. 85 parts by mass of 1.0 mol / L CaCl2 aqueous solution were gradually added to the resulting mixture. Thus, an aqueous dispersion medium containing the finely dispersed, sparingly soluble, water-soluble dispersion stabilizer Ca3(PO4)2 was prepared.

[0284] Subsequently, a toner particle precursor composition was produced using the following materials.

[0285]

[0286] (Aluminum compounds of 3,5-di-tert-butylsalicylic acid)

[0287] • Release agent (behenate behenate): 10.0 parts by weight

[0288] The above materials were dissolved in 400 parts by mass of toluene, and the temperature of the solution was raised to 63°C. This yielded a toner particle precursor composition.

[0289] Next, the toner particle precursor composition was added to an aqueous dispersion medium containing finely ground water-insoluble dispersion stabilizer Ca3(PO4)2, and the mixture was granulated for 5 minutes while being stirred at 12,000 rpm using a high-speed mixer. Then, the high-speed mixer was replaced with a propeller mixer, and the temperature inside the container was raised to 70°C. The heating time was 10 minutes. The granulated product was then allowed to react for 5 hours while being slowly stirred. Afterward, the temperature was raised to 95°C, and the product was heated at this temperature for 5 hours to allow the reaction to proceed. This yielded a slurry of toner particles.

[0290] The washing and drying steps after the reaction were carried out in the same manner as in the production example of toner particles 1, toner particles 2 were obtained. The weight-average particle size of the obtained toner particles 2 was 6.2 μm.

[0291] [Production example of colorant granules 3]

[0292] The aqueous medium preparation step, the polymerizable monomer composition preparation step, and the granulation step are carried out in the same manner as in the production example of colorant granules 1.

[0293] <Preparation steps of organosilicon compound aqueous solution 1>

[0294] Weigh 60.0 parts of ion-exchanged water into a reaction vessel including a stirrer and a thermometer, and adjust its pH to 1.5 with 10% hydrochloric acid by mass. While stirring the result, heat it to a temperature of 80°C. Then, add 40.0 parts of methyltriethoxysilane to the heated product, and stir the mixture for 5 minutes to provide an aqueous solution of the organosilicon compound.

[0295] <Aggregation Steps>

[0296] The mixer was replaced with a propeller-type mixer, and polymerization was carried out for 5 hours while the granulated product was stirred at 150 rpm and kept at 70°C. The temperature was then increased to 95°C, and the product was heated at this temperature for 5 hours to allow the polymerization reaction to proceed. This yielded a slurry of toner particles. The slurry was then cooled to 60°C, and its pH was measured. The pH was found to be 5.0. While stirring the slurry at 60°C, 30.0 parts of an aqueous solution of an organosilicon compound were added. The slurry was kept as is for 30 minutes, and then the pH was adjusted to 9.0 with an aqueous sodium hydroxide solution. The resulting product was further kept for 300 minutes to form an organosilicon polymer on the surface of each toner particle.

[0297] The washing and drying steps following the polymerization step were performed in the same manner as in the production example of toner particles 1, to obtain toner particles 3. The weight-average particle size of the obtained toner particles 3 was 6.3 μm.

[0298] [Production example of toner 1]

[0299] 100.0 parts of toner granules 1 and 2.0 parts of approximately hemispherical fine particles 1 were dry-mixed for 5 minutes using an FM MIXER (manufactured by Nippon Coke & Engineering Co., Ltd.). Furthermore, the added particles were sieved through a sieve with a pore size of 150 μm. Toner 1 was thus obtained. The physical properties of the obtained toner are shown in Table 3.

[0300] [Production examples of toners 2 to 22 and comparative toners 1 to 4]

[0301] Except for using the formulations shown in Table 3, toners 2 to 22 and comparative toners 1 to 4 were obtained in the same manner as in the production example of toner 1. The physical properties of the obtained toners are shown in Table 3.

[0302] [Comparison Toner 5]

[0303] The original colorant granules 3 were used as the comparative colorant 5.

[0304] Table 3

[0305]

[0306] [Image Output Evaluation]

[0307] <Evaluation of Cleanliness>

[0308] A tandem laser beam printer (product name: LBP9600C, hereinafter sometimes referred to as "LBP9600C") manufactured by Canon Inc. was modified to print only using the cyan station. The toner cartridge for the LBP9600C was filled with 120g of toner to be evaluated, and the entire toner cartridge was placed in a low-temperature, low-humidity (L / L) (10℃ / 15%RH) environment for 24 hours. After 24 hours, the toner cartridge was installed on the LBP9600C, and the toner loading on image receiver paper 18 was 0.25mg / cm³. 2 A halftone image was then printed. Subsequently, 14,000 A4 sheets were printed horizontally at a print rate of 1.0%. Image output was performed in a low-temperature, low-humidity environment (15°C / 10% RH). This condition is more demanding for cleaning due to the increased hardness of the cleaning blade, reducing its tracking ability towards the photosensitive drum 1. After 14,000 prints, a toner loading of 0.25 mg / cm³ was output on the image receiving paper 18. 2 Halftone images. The following criteria were used to evaluate the images and charging roller contamination before (initial) and after 14,000 output images (after durability evaluation). A CS-680 (sold by Canon Marketing Japan Inc., basis weight: 68g / m³) was used. 2 ) as image receiving paper 18.

[0309] A: There is no cleaning defect on the halftone image and no contamination on the charging roller.

[0310] B: There is no cleaning defect on the halftone image, but there is contamination on the charging roller.

[0311] C: Extremely fine vertical lines are observed in the halftone image as poor cleaning.

[0312] D: 1 to 9 clear vertical lines are observed on the halftone image as poor cleaning.

[0313] E: More than ten clear vertical lines were observed on the halftone image as poor cleaning.

[0314] In this invention, a standard of C or higher is considered satisfactory.

[0315] <Evaluation of Low-Temperature Fixing Performance>

[0316] The fixing unit of the LBP9600C was modified to allow for adjustment of the fixing temperature. While varying the fixing temperature from 140°C in 5°C increments, images were output using the modified LBP9600C at a processing speed of 320 mm / sec. Image output was conducted in a low-temperature, low-humidity environment (15°C / 10% RH), which is more demanding for low-temperature fixing due to the difficulty in raising the fixing unit's temperature. Using the toner to be evaluated, a toner loading of 0.40 mg / cm³ was formed on the image receiving paper. 2 A solid image is formed and fixed on image receiving paper by heating and pressurizing in an oil-free manner. KimWipes (S-200, manufactured by Crecia Co., Ltd.) at 75 g / cm³ is used. 2 The fixed image was rubbed ten times under a load, and the temperature at which the image density reduction rate before and after rubbing became less than 10% was defined as the fixing temperature. The image was then evaluated based on the following criteria.

[0317] Use A4 paper (product name: Ocean Label, manufactured by Canon Inc., basis weight: 80g / m²). 2 The image receiving paper was used. A color reflectance densitometer X-RITE 404A (manufactured by X-Rite Inc.) was used for image density measurement, and the density of the printed image in the white background area relative to the original density of 0.00 was measured. The rate of decrease in image density after rubbing was then calculated.

[0318] A: Fixing temperature is less than 150℃.

[0319] B: Fixing temperature is above 150℃ and below 156℃.

[0320] C: Fixing temperature is above 156℃ and below 162℃.

[0321] D: Fixing temperature is above 162℃ and below 170℃.

[0322] E: Fixing temperature is above 170℃.

[0323] In this invention, a grade of D or higher is considered satisfactory.

[0324] <Evaluation of component contamination>

[0325] Using the same method as the cleanliness evaluation, images with a print rate of 1.0% were printed horizontally on 14,000 sheets of A4 paper under low temperature and low humidity (L / L) (10℃ / 15%RH) conditions. After printing 14,000 sheets, the toner loading on the image receiving paper was 0.25 mg / cm³. 2The halftone image. The density of the central part and the left and right ends (30 mm from each end of the paper) of the halftone image is measured, and the density difference is calculated. Then, it is evaluated based on the following criteria.

[0326] It is known that when the charging component is contaminated, uneven charging will occur on the photosensitive component, resulting in uneven density in halftone images.

[0327] Use CS-680 (sold by Canon Marketing Japan Inc., basis weight: 68g / m³). 2 The image receiving paper was used. A color reflectance densitometer X-RITE 404A (manufactured by X-Rite Inc.) was used for image density measurement, and the density of the printed image in the white background area with a density of 0.00 relative to the original was measured. The density difference between the center of the image and its various ends was then calculated.

[0328] A: The density difference of the halftone image after durability evaluation is less than 0.03.

[0329] B: The density difference of the halftone image after durability evaluation is greater than 0.03 and less than 0.05.

[0330] C: The density difference of the halftone image after durability evaluation is greater than 0.05 and less than 0.10.

[0331] D: The density difference of the halftone image after durability evaluation is greater than 0.10.

[0332] In this invention, grades C and above are considered satisfactory.

[0333] [Examples 1 to 22 and Comparative Examples 1 to 5]

[0334] For each toner shown in Table 3, which has the fine particles shown in Tables 1 and 2 on its surface, cleanliness, low-temperature fixing, and component contamination were evaluated after initial and durability assessments. The results are shown in Table 4.

[0335] Table 4

[0336]

[0337] Although the invention has been described with reference to exemplary embodiments, it should be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the appended claims is to be interpreted in the broadest possible sense, covering all such modifications and equivalent structures and functions.

Claims

1. A toner comprising: Colorant granules containing binder resin and colorant; and Fine particles on the surface of the toner particles, The fine particles are characterized in that they are solid and generally hemispherical, and have a generally flat surface and curved surfaces. When the surface of the toner particles is observed, the generally flat surface of the fine particles is observed, and The average number of longest diameters "w" on the generally flat surface is between 10 and 400 nm. When observing a cross-section intersecting the generally flat surface of the fine particles, The line connecting the two intersection points Pa and Pb of the line Lf originating from the generally flat surface and the line Lc originating from the curved surface is defined as the imaginary line Li. In line Ls1, which intersects the imaginary line Li perpendicularly, the maximum height "h" is defined as the maximum distance between two points, Da and Db, where point Pc is the intersection of imaginary line Li and line Ls1, point Pe is the intersection of line Lc and line Ls1, and point Pd is the intersection of line Lf and line Ls1. and In line Ls2, which is parallel to the imaginary line Li, the maximum distance Dc between the two intersection points Pf and Pg of line Ls2 and line Lc is defined as the maximum width "b". The average number of ratios h / b of the maximum height "h" to the maximum width "b" is between 0.33 and 0.

80.

2. The toner according to claim 1, wherein the fine particles comprise at least one structure selected from the group consisting of structures represented by formulas (D), (T), and (Q): (Ra)(Rb)Si(O 1 / 2 )2 Formula (D) Rc-Si(O 1 / 2 )3 formula (T) Si(O 1 / 2 )4 formula (Q) In formulas (D), (T) and (Q), Ra, Rb and Rc each represent an organic group bonded to silicon.

3. The toner according to claim 1 or 2, wherein the toner comprises 0.1 parts by mass or more of fine particles on the surface of the toner particles.

4. An external additive for colorants, characterized in that, It is solid and roughly hemispherical, with a generally flat surface and curved surfaces. The average number of longest diameters "w" on the generally flat surface is between 10 and 400 nm. Specifically, when observing a cross-section intersecting a generally flat surface with the external additive used in the colorant, The line connecting the two intersection points Pa and Pb of the line Lf originating from the generally flat surface and the line Lc originating from the curved surface is defined as the imaginary line Li. In line Ls1, which intersects the imaginary line Li perpendicularly, the maximum height "h" is defined as the maximum distance between two points, Da and Db, where point Pc is the intersection of imaginary line Li and line Ls1, point Pe is the intersection of line Lc and line Ls1, and point Pd is the intersection of line Lf and line Ls1. and In line Ls2, which is parallel to the imaginary line Li, the maximum distance Dc between the two intersection points Pf and Pg of line Ls2 and line Lc is defined as the maximum width "b". The average number of ratios h / b of the maximum height "h" to the maximum width "b" is between 0.33 and 0.

80.

5. The external additive for toner according to claim 4, wherein the external additive for toner comprises at least one structure selected from the group consisting of structures represented by formulas (D), (T), and (Q): (Ra)(Rb)Si(O 1 / 2 )2 Formula (D) Rc-Si(O 1 / 2 )3 formula (T) Si(O 1 / 2 )4 formula (Q) In formulas (D), (T) and (Q), Ra, Rb and Rc each represent an organic group bonded to silicon.

6. A fine particle, characterized in that, It is solid and roughly hemispherical, with a generally flat surface and curved surfaces. The average number of longest diameters "w" on the generally flat surface is between 10 and 400 nm. When observing a cross-section intersecting the generally flat surface of the fine particles, The line connecting the two intersection points Pa and Pb of the line Lf originating from the generally flat surface and the line Lc originating from the curved surface is defined as the imaginary line Li. In line Ls1, which intersects the imaginary line Li perpendicularly, the maximum height "h" is defined as the maximum distance between two points, Da and Db, where point Pc is the intersection of imaginary line Li and line Ls1, point Pe is the intersection of line Lc and line Ls1, and point Pd is the intersection of line Lf and line Ls1. and In line Ls2, which is parallel to the imaginary line Li, the maximum distance Dc between the two intersection points Pf and Pg of line Ls2 and line Lc is defined as the maximum width "b". The average number of ratios h / b of the maximum height "h" to the maximum width "b" is between 0.33 and 0.

80.

7. The fine particles according to claim 6, wherein the fine particles comprise at least one structure selected from the group consisting of structures represented by formulas (D), (T), and (Q): (Ra)(Rb)Si(O 1 / 2 )2 Formula (D) Rc-Si(O 1 / 2 )3 formula (T) Si(O 1 / 2 )4 formula (Q) In formulas (D), (T) and (Q), Ra, Rb and Rc each represent an organic group bonded to silicon.

Images