JP2018194836A - toner - Google Patents

Abstract

To provide a toner which prevents thin paper from winding around a fixing device even at low temperature fixing, and prevents transfer roughness even after durability under high temperature and high humidity environment.SOLUTION: A toner has toner particles having a binder resin and a release agent, where the toner particles have a surface layer containing an organic silicon polymer, brightness histogram of a reflection electron image of the toner particles have two maximal values P1 and P2 and a minimum value V between P1 and P2, P2 is derived from the organic silicon polymer, brightness giving P1 and P2 is within a specific range, ratios of P1 and P2 are each 0.50% or more, and when the total pixel number of brightness 0 or more and (Bl-30) or less is represented by A1, the total pixel number of brightness (Bl-29) or more and (Bl+29) or less is represented by AV, and the total pixel number of brightness (Bl+30) or more and 255 or less is represented by A2, based on brightness Bl of V, A1, AV and A2 satisfy a specific relationship.SELECTED DRAWING: None

Description

  The present invention relates to a toner for developing an electrostatic image used in an image forming method such as electrophotography and electrostatic printing.

In recent years, laser beam printers and copiers are required to have lower power consumption and higher image quality. In response to this requirement, various studies have been made in order to develop a toner having excellent low-temperature fixability and development transferability.
Among them, a toner has been proposed in which thin paper does not wrap around a heating member of a fixing device while maintaining low-temperature fixability. Japanese Patent Application Laid-Open No. H11-260260 discloses a technique for suppressing winding by covering core particles with a resin shell layer and forming certain holes in the shell layer. However, since the resin shell layer alone has problems in development transferability from the viewpoint of fluidity and chargeability, an external additive is required. On the other hand, since the external additive becomes a problem of embedding and detachment with continuous use, there is still room for improvement in terms of durability.
Therefore, Patent Document 2 proposes a toner having both a coating layer of a silane compound and externally added inorganic particles as a technique for improving charging stability and improving durability.

JP 2009-186640 A Japanese Patent No. 5407377

However, in the technique described in Patent Document 2, the inhibition of fixability due to the high coverage of the toner base particles is not negligible, and there is still a problem in winding thin paper around the fixing device particularly at low temperatures. It was.
An object of the present invention is a toner that achieves both low-temperature fixability and development transferability after continuous use. Specifically, it is difficult for thin paper to wrap around a fixing device during low-temperature fixing, and is durable in a high-temperature and high-humidity environment. It is to provide a toner that is less likely to cause transfer bosses later.

The present invention is a toner having toner particles having a binder resin and a release agent,
The toner particles have a surface layer containing an organosilicon polymer,
In the scanning electron microscope observation of the surface of the toner particle, a reflected electron image of 1.5 μm square on the surface of the toner particle is obtained, and the luminance of each pixel constituting the reflected electron image is 256 gradations from luminance 0 to luminance 255. And obtaining a luminance histogram with the horizontal axis representing the luminance and the vertical axis representing the number of pixels,
(I) There are two maximum values P1 and P2 and a minimum value V between P1 and P2, and the peak containing P2 is a peak derived from the organosilicon polymer,
(Ii) The luminance giving P1 is 20 or more and 70 or less,
(Iii) The luminance giving P2 is 130 or more and 230 or less,
(Iv) The ratio of P1 and P2 to the total number of pixels of the reflected electron image is 0.50% or more,
(V) The luminance giving V is B1, the total number of pixels in the luminance range 0 to (Bl-30) is A1, the total number of pixels in the luminance range (Bl-29) to (Bl + 29) is AV, the luminance range ( B1 + 30) to 255, where A2 is the total number of pixels, the following formulas (1) and (2)
(A1 / AV) ≧ 1.50 (1)
(A2 / AV) ≧ 1.50 (2)
Meet,
This invention relates to a toner.

  According to the present invention, it is possible to provide a toner that hardly causes a thin paper to be wound around a fixing device during low-temperature fixing, and that does not easily generate a transfer margin even after endurance in a high-temperature and high-humidity environment.

Example of luminance histogram obtained from the backscattered electron image of the toner particle surface Example of toner particle surface reflection electron image and binarized image showing presence or absence of network structure Schematic configuration diagram showing an example of an image forming apparatus

In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
Hereinafter, the present invention will be described in detail.
The present invention is a toner having toner particles having a binder resin and a release agent,
The toner particles have a surface layer containing an organosilicon polymer,
In the scanning electron microscope observation of the surface of the toner particle, a reflected electron image of 1.5 μm square on the surface of the toner particle is obtained, and the luminance of each pixel constituting the reflected electron image is 256 gradations from luminance 0 to luminance 255. And obtaining a luminance histogram with the horizontal axis representing the luminance and the vertical axis representing the number of pixels,
(I) There are two maximum values P1 and P2 and a minimum value V between P1 and P2, and the peak containing P2 is a peak derived from the organosilicon polymer,
(Ii) The luminance giving P1 is 20 or more and 70 or less,
(Iii) The luminance giving P2 is 130 or more and 230 or less,
(Iv) The ratio of P1 and P2 to the total number of pixels of the reflected electron image is 0.50% or more,
(V) The luminance giving V is B1, the total number of pixels in the luminance range 0 to (Bl-30) is A1, the total number of pixels in the luminance range (Bl-29) to (Bl + 29) is AV, the luminance range ( B1 + 30) to 255, where A2 is the total number of pixels, the following formulas (1) and (2)
(A1 / AV) ≧ 1.50 (1)
(A2 / AV) ≧ 1.50 (2)
Meet,
It is characterized by that.

As will be described later, the reflected electron image acquisition condition in the present invention is set so as to reflect the outermost surface of the toner particles. Under the acquisition conditions, the electron beam entry region and the X-ray generation region for each element estimated from the Kanaya-Okayama equation are approximately several tens of nm. In the present invention, in a scanning electron microscope observation of the surface of a toner particle having a surface layer containing an organosilicon polymer, a reflected electron image of 1.5 μm square on the surface of the toner particle is obtained. The luminance of each pixel constituting the reflected electron image is divided into 256 gradations from luminance 0 to luminance 255, and a luminance histogram is obtained with the horizontal axis representing the luminance and the vertical axis representing the number of pixels. At this time, in the luminance histogram, it is essential that there are two maximum values P1 and P2 and a minimum value V between P1 and P2.
In the luminance histogram, the lower one is darker (black) and the higher one is bright (white). The reflected electron image obtained from the scanning electron microscope is also called a “composition image”, and the smaller the atomic number, the darker the image, and the larger the brighter the image, the brighter the detected image. Since the toner particles have an organosilicon polymer on the surface, the peak including the maximum value P1 having a low luminance is derived from the base of the toner particles, and the peak including the maximum value P2 having the high luminance is derived from the organosilicon polymer.

  The matrix here refers to a carbon-based composition such as a binder resin or a release agent contained in the toner particles. Moreover, it can confirm that the peak containing P2 originates in an organosilicon polymer by superimposing the elemental mapping image by energy dispersive X-ray analysis (EDS) which can be acquired by scanning electron microscope observation, and the reflected electron image. . One of the requirements of the present invention is such a bimodal histogram having P1 derived from the base of the toner particles, P2 derived from the organosilicon polymer, and a minimum value V between P1 and P2 ( For example, FIG. 1 (a)). As shown in FIG. 1B, when the luminance histogram has a single maximum value (P1 or P2) and does not have the minimum value V, the requirement of the present invention is not satisfied.

It is also important that the luminance that gives P1 is 20 or more and 70 or less and the luminance that gives P2 is 130 or more and 230 or less. When the luminances of P1 and P2 are separated to some extent and the luminances of P1 and P2 are within a certain range, there is little overlap between peak 1 having the maximum value P1 and peak 2 having the maximum value P2, and separation is not possible. It becomes good. “Luminance that gives P1” or “Luminance that gives P2” means the luminance when the number of pixels takes the maximum value P1 or the maximum value P2, respectively.
As described above, the peak including P1 is derived from the base of the toner particles, and the peak including P2 is derived from the organosilicon polymer. When the separation between the peaks 1 and 2 is good, the base of the toner particles and the organosilicon polymer are efficiently localized on the surface of the toner particles, and the functions described later are more effectively exhibited. The luminance that gives P1 is preferably 20 or more and 60 or less, and the luminance that gives P2 is preferably 140 or more and 230 or less.

Further, it is necessary that the ratio of P1 and P2 to the total number of pixels of the reflected electron image is 0.50% or more.
Further, the luminance that gives the minimum value V is Bl, the total number of pixels in the luminance range 0 to (Bl-30) is A1, the total number of pixels in the luminance range (Bl-29) to (Bl + 29) is AV, the luminance range ( B1 + 30) to 255, where A2 is the total number of pixels, the following formulas (1) and (2)
(A1 / AV) ≧ 1.50 (1)
(A2 / AV) ≧ 1.50 (2)
Satisfying the requirement is an essential requirement (for example, FIG. 1A). In the case of the luminance histogram as shown in FIG. 1C which does not have the relationship of the above formulas (1) and (2), the requirement of the present invention is not satisfied. Here, the number of pixels A1 having a luminance range of 0 or more (Bl-30) or less is mainly composed of peak 1 having P1 as a maximum value, and the number of pixels A2 having a luminance range (Bl + 30) or more and 255 or less is maximal. The peak 2 as a value is the main component. As described above, P1 is derived from the toner particle matrix, and P2 is derived from the organosilicon polymer. Therefore, each pixel included in A1 belongs to the toner particle matrix, and each pixel included in A2 belongs to the organosilicon polymer. Is done.

That is, the larger P1 and the larger A1, the more the matrix component is present on the toner particle surface, and the larger P2 and the larger A2, the more organosilicon polymer component is present on the toner particle surface. As a result, a toner that does not easily wrap thin paper around the fixing device even during low-temperature fixing, and that does not easily generate transfer even after endurance in a high-temperature and high-humidity environment is achieved.
If the base component of the toner particles is sufficiently present on the surface of the toner particles, the release agent oozes from the base of the toner particles easily even when the fixing temperature is low. It is known that thin paper is easy to wind. However, when an appropriate amount of a release agent oozes out from a base of toner particles during fixing, separation of the fixing member and the thin paper is facilitated. The ratio of P1 to the total number of pixels of the reflected electron image is 0.50% or more, and the following formula (1)
(A1 / AV) ≧ 1.50 (1)
When satisfying the condition, the effect of suppressing thin paper wrapping around the fixing device at the time of low-temperature fixing is exhibited. From the viewpoint of thin paper wrapping property at low-temperature fixing, a preferable condition is that the ratio of P1 to the total number of pixels of the reflected electron image is 0.70% or more and 5.00% or less, and the following formula (3)
4.00 ≧ (A1 / AV) ≧ 1.70 (3)
Is to satisfy.

On the other hand, if the organosilicon polymer component is sufficiently present on the surface of the toner particles, the non-electrostatic adhesion to the photosensitive drum, intermediate transfer member and other members can be kept low even during transfer in a high temperature and high humidity environment. be able to. When the non-electrostatic adhesive force is small, the response to the transfer voltage is increased, so that the transfer boss is hardly generated.
The term “transfer boss” as used herein refers to an image defect in which the in-plane uniformity of the image is reduced because there is toner that is not transferred in some places when an image having a uniform density is output. Depending on the polymerization conditions, the organosilicon polymer can form unevenness of several tens to hundreds of nanometers from fine unevenness of several nm level while maintaining the coverage on the toner particle surface at a certain level or more. In addition, although the detailed chemical structure will be described later, since the organosilicon polymer preferably has a hydrophobic organic group such as a hydrocarbon group, the surface energy is low.

Although the mechanism is not clear, it is considered that the presence of the organosilicon polymer on the surface of the toner particles serves as an efficient spacer, reducing the frequency and adhesion of the toner particle base to the member. As a preferred embodiment, when a hydrophobic organic group such as a hydrocarbon group is present in the organosilicon polymer, the charging stability in a high temperature and high humidity environment is also improved. In addition, the organosilicon polymer preferably has a siloxane bond, so that it can be present on the toner particle surface as a surface layer having a strong covalent bond, so that durability durability is superior to that of the external additive.
In the present invention, the ratio of P2 to the total number of pixels of the reflected electron image is 0.50% or more, and the following formula (2)
(A2 / AV) ≧ 1.50 (2)
When satisfying, it exhibits the effect of suppressing the transfer boss after endurance in a high-temperature and high-humidity environment. Further, the ratio of P2 to the total number of pixels of the reflected electron image is 0.70% or more and 5.00% or less, and the following formula (4)
4.00 ≧ (A2 / AV) ≧ 1.70 (4)
If it satisfies, it is more effective in suppressing the transfer margin after endurance in a high temperature and high humidity environment, which is preferable.

  Here, AV in the formulas (1) to (4) will be described. As described above, when the luminance histogram of the backscattered electron image is bimodal, the state where the two peaks derived from the toner particle matrix and the organosilicon polymer are independent is an ideal form of the present invention. . In that case, there is almost no overlap between the two peaks, and the AV including the minimum value V becomes extremely small. However, in practice, a luminance histogram in which two peaks are connected is obtained, and AV has a certain number of pixels. At this time, each pixel included in the AV is a gray value including components of both the matrix and the organosilicon polymer that have flowed in from A1 and A2.

Specifically, when the organosilicon polymer is present as a thin film of several nanometers on the surface of the toner particle matrix, the low melting point / low molecular components derived from the toner particle matrix are filmed on the surface of the organosilicon polymer. This is the case. In such a case, the effects of the matrix and the organosilicon polymer are reduced compared to the case where the matrix of the toner particles and the organosilicon polymer are localized with high purity.
As AV is smaller, A1 and A2 increase, and the base of the toner particles and the organosilicon polymer are more efficiently localized, respectively. That is, it is possible to achieve a toner that hardly causes thin paper to be wound around the fixing device even during low-temperature fixing, and that does not easily generate a transfer margin even after durability under a high-temperature and high-humidity environment.
The brightness and the number of pixels that give P1 and P2, the brightness Bl that gives the minimum value V, and the number of pixels A1, A2, and AV are the monomer type of the organosilicon polymer, the reaction temperature and reaction during the formation of the organosilicon polymer. Control is possible by time, reaction solvent and pH.

It is preferable that the organosilicon polymer on the toner particle surface has a network structure in which particles composed of pixels having a luminance range of 0 or more (Bl-30) or less are formed on the toner particle surface. That is, the organosilicon polymer forms a network structure on the surface of the toner particles. In the reflected electron image, all the pixels are divided into a pixel group A having a luminance range of 0 or more (Bl-30) and a luminance range ( B1-29) When the pixel group B is divided into 255 or less pixel group B, it is preferable that the network structure of the pixel group B with the pixel group A as a mesh is observed.
The domain formed by the pixel group A (particles composed of pixels having a luminance of 0 or more (Bl-30) or less (hereinafter also referred to as particles A1)) has an area number average value of 2.00 × 10. It is preferably ³ nm ² or more and 1.00 × 10 ⁴ nm ² or less, and the number average value of the ferret diameter is preferably 60 nm or more and 200 nm or less. More preferably, the number average value of the area is 2.00 × 10 ³ nm ² or more and 8.00 × 10 ³ nm ² or less, and the number average value of the ferret diameter is 60 nm or more and 150 nm or less.

As described above, A1 belongs to the base of toner particles. When the organosilicon polymer on the toner particle surface has a network structure, as shown in FIG. 2A, pixel portions (white) having luminance (Bl-29) or more and 255 or less form a network. The domain (particle A1) portion composed of the pixel portion (black) having a luminance of 0 or more (Bl-30) or less without the organosilicon polymer forms a “network” of the network structure, and is an isolated particle It is detected as follows.
Although the detailed method will be described later, the size of the “mesh” of the network structure is expressed by performing particle analysis on the domain (particle A1) formed by the pixel group A and calculating the area and the ferret diameter. can do. At the time of fixing, the binder resin melts and the release agent oozes out from the part of the particle A1, which is the base part of the toner particles.

In other words, when the area of the domain (particle A1) formed by the pixel group A and the diameter of the ferret have a certain size, melting of the binder resin from the base of the toner particles and exudation of the release agent are appropriate at the time of fixing. To happen. Thereby, a toner excellent in low-temperature fixability can be obtained. Here, the ferret diameter is the distance of the longest of straight lines connecting two arbitrary points on the boundary line on the outer periphery of the selection range. When the particle area is 2.00 × 10 ³ nm ² or more, or the ferret diameter is 60 nm or more, the binder resin melts and the release agent oozes out, which is particularly advantageous for low-temperature fixability from the viewpoint of blistering. It is.
On the other hand, when the area of the domain formed by the pixel group A is 1.00 × 10 ⁴ nm ² or less, or the ferret diameter is 200 nm or less, melting of the binder resin and exudation of the release agent are appropriate. In particular, it is advantageous for low-temperature fixability from the viewpoint of hot offset.
The area and the ferret diameter of the domain formed in the pixel group A can be controlled by the monomer type of the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent, and the pH when forming the organosilicon polymer.
It can be confirmed by the following method that the organosilicon polymer on the toner particle surface forms a network structure having the pixel group A as a mesh. When a binarized image in which a pixel portion having a luminance range of 0 or more (Bl-30) or less is obtained from the reflected electron image and has a shape as shown in FIG. It is determined that the silicon polymer forms a network structure.
On the other hand, as shown in FIG. 2B, when the organosilicon polymer on the surface of the toner particles does not have a network structure, the pixel portion (white) having a luminance range (Bl-29) or more and 255 or less is like an isolated particle. Detected. And the particle | grains A1 comprised from the pixel part (black) of the luminance range 0 or more (Bl-30) or less without an organosilicon polymer form a net | network. That is, when the organosilicon polymer on the toner particle surface does not form a network having a network structure, the area and the ferret diameter of the particle A1 tend to increase.
In the present invention, the organosilicon polymer is preferably a polymer having a structure represented by the following formula (RaT3).

(In the formula, Ra represents a hydrocarbon group having 1 to 6 carbon atoms (preferably an alkyl group), or a vinyl polymer part including a partial structure represented by formula (i) or formula (ii)). (In the formulas (i) and (ii), * represents a bonding site with an Si element in the RaT3 structure, and L in the formula (ii) is an alkylene group (preferably a methylene group) or an arylene group (preferably a phenylene group). ) Represents)))

Of the four valence electrons of the Si atom in the above formula (RaT3), one is involved in the bond with Ra and the remaining three are involved in the bond with the O atom. The O atom constitutes a state in which two valence electrons are both involved in the bond with Si, that is, a siloxane bond (Si—O—Si). Considering Si atoms and O atoms as an organosilicon polymer, two Si atoms and three O atoms are expressed as —SiO _3/2 .
If one of the oxygens is a silanol group, the structure of the organosilicon polymer is represented by —SiO _2/2 —OH. Furthermore, if two oxygens are silanol groups, the structure is —SiO _1/2 (—OH) ₂ . When these structures are compared, it is closer to the silica structure represented by SiO ₂ when more oxygen atoms form a crosslinked structure with Si atoms. Therefore, the more the —SiO _3/2 skeleton, the lower the surface free energy on the surface of the toner particles, and the more excellent the environmental stability and anti-member contamination.

Further, since Ra is a hydrophobic organic group, the surface free energy on the surface of the toner particles is kept low even by the presence of Ra, and the effect of excellent environmental stability is exhibited.
Presence of the siloxane polymer part (—SiO _3/2 ) in the formula (RaT3) can be confirmed by ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble part of the toner particles. The presence of Ra in the formula (RaT3) can be confirmed by measurement of ¹³ C-NMR of the tetrahydrofuran insoluble matter in the toner particles.
The structure can be controlled by the kind and amount of the monomer type of the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent, and the pH when forming the organosilicon polymer.

  A sol-gel method can be given as an example of producing an organosilicon polymer. In the sol-gel method, a metal alkoxide M (OR) n (M: metal, O: oxygen, R: hydrocarbon, n: oxidation number of metal) is used as a starting material, and hydrolysis and polycondensation are carried out in a solvent. It is a method of gelling through the state. Used in methods for synthesizing glass, ceramics, organic-inorganic hybrids, and nanocomposites. By using this production method, functional materials having various shapes such as surface layers, fibers, bulk bodies, and fine particles can be produced from a liquid phase at a low temperature. The organosilicon polymer is preferably produced by hydrolysis and condensation polymerization of a silicon compound typified by alkoxysilane (preferably a compound represented by the following formula (Z)).

Furthermore, since the sol-gel method forms a material by starting from a solution and gelling the solution, various microstructures and shapes can be created. In particular, when the toner particles are produced in an aqueous medium, they are likely to be present on the surface of the toner particles due to hydrophilicity due to hydrophilic groups such as silanol groups of the organosilicon compound. The fine structure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, type and amount of silicon compound, and the like.
In general, it is known that in the sol-gel reaction, the bonding state of siloxane bonds generated varies depending on the acidity of the reaction medium. Specifically, when the reaction medium is acidic, hydrogen ions are electrophilically added to oxygen of one reactive group (for example, an alkoxy group). Next, the oxygen atom in the water molecule is coordinated to the silicon atom and becomes a hydroxy group by a substitution reaction. When water is sufficiently present, one hydrogen ion attacks one oxygen of the reactive group (for example, an alkoxy group). As the reaction proceeds, the content of hydrogen ions in the medium and the reactive group decrease. As a result, the substitution reaction with the hydroxy group becomes slow. Therefore, a polycondensation reaction occurs before all of the reactive groups attached to the silane are hydrolyzed, and a one-dimensional linear polymer or a two-dimensional polymer is easily generated relatively easily.

On the other hand, when the medium is alkaline, hydroxide ions are added to silicon and go through a pentacoordinate intermediate. For this reason, all reactive groups (for example, alkoxy groups) are easily removed and easily substituted with silanol groups. In particular, when a silicon compound having three or more reactive groups on the same silane is used, hydrolysis and polycondensation occur three-dimensionally to form an organosilicon polymer having a large number of three-dimensional crosslinks. . The reaction is also completed in a short time.
Therefore, in order to form the organosilicon polymer, it is preferable to proceed the sol-gel reaction with the reaction medium being in an alkaline state. Specifically, when producing in an aqueous medium, the pH should be 8.0 or more. preferable. As a result, an organosilicon polymer having higher strength and superior durability can be formed.

  The organosilicon polymer on the toner particle surface is preferably a polycondensation product of an organosilicon compound having a structure represented by the following formula (Z).

(In the formula (Z), Ra represents a hydrocarbon group. R ¹ , R ² and R ³ each independently represent a halogen atom, a hydroxy group, an acetoxy group, or (preferably having a carbon number of 1 or more and 3 The following represents an alkoxy group.)
Ra is a functional group that becomes Ra in the RaT3 structure, and includes a structure represented by the following formula (iii) or the following formula (iv). Ra is particularly preferably an alkyl group having 1 to 6 carbon atoms.

(In the formulas (iii) and (iv), * represents a bonding site with the Si element in the Z structure, and L in the formula (iv) represents an alkylene group (preferably a methylene group) or an arylene group (preferably a phenylene group). Group).)
Hydrophobicity can be improved by the organic group of Ra, and toner particles excellent in environmental stability can be obtained. A phenyl group which is an aromatic hydrocarbon group can also be used as the aryl group.

R ¹ , R ² and R ³ are each independently a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups are hydrolyzed, addition-polymerized and condensation-polymerized to form a crosslinked structure, and a toner having excellent resistance to member contamination and development durability can be obtained. From the viewpoints of moderate hydrolyzability at room temperature, precipitation on the surface of the toner particles and coverage, an alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. Further, hydrolysis, addition polymerization and condensation polymerization of R ¹ , R ² and R ³ can be controlled by reaction temperature, reaction time, reaction solvent and pH.
In order to obtain an organosilicon polymer, an organosilicon compound having _three reactive groups (R ₁ , R ₂ and R ₃ ) in one molecule excluding Ra in the formula (Z) (hereinafter also referred to as trifunctional silane). May be used alone or in combination.

Examples of the formula (Z) include the following.
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyl Triacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxy Hydroxysilane, vinylethoxymethoxyhydroxysila Trifunctional vinyl silanes, such as vinyldiethoxyhydroxysilane; allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, allylethoxydimethoxysilane, allyltrichlorosilane, allylmethoxydichlorosilane, allylethoxydichlorosilane , Allyldimethoxychlorosilane, allylmethoxyethoxychlorosilane, allyldiethoxychlorosilane, allyltriacetoxysilane, allyldiacetoxymethoxysilane, allyldiacetoxyethoxysilane, allylacetoxydimethoxysilane, allylacetoxymethoxyethoxysilane, allylacetoxydiethoxysilane, allyl Trihydroxysilane, allylmethoxydihydroxysilane, allylethoxydihydroxysilane, Trifunctional allylsilanes such as rildimethoxyhydroxysilane, allylethoxymethoxyhydroxysilane, allyldiethoxyhydroxysilane; p-styryltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methyl Ethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methyl Acetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane , Trifunctional methylsilanes such as methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane; ethyltrimethoxysilane, ethyltrimethoxysilane Trifunctional ethylsilanes such as ethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, Trifunctional propylsilanes such as: butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltri Trifunctional butylsilanes such as cetoxysilane, butyltrihydroxysilane; trifunctional hexylsilanes such as hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane; Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane. An organosilicon compound may be used independently and may use 2 or more types together.

As a result of hydrolysis and polycondensation, the content of the organosilicon compound having a structure represented by the formula (Z) in the organosilicon polymer is preferably 50 mol% or more, more preferably 60 mol% or more. .
In addition to the organosilicon compound having the structure represented by the formula (Z), an organosilicon compound having four reactive groups in one molecule (tetrafunctional silane) and an organic having three reactive groups in one molecule A silicon compound (trifunctional silane), an organosilicon compound having two reactive groups in one molecule (bifunctional silane), or an organosilicon compound having one reactive group (monofunctional silane) may be used in combination. . For example, the following can be mentioned.

Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino Til) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- Chloropropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, trimethylsilyl Chloride, triethylsilyl chloride, triisopropylsilyl chloride, t-butyldimethylsilyl chloride, N, N′-bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) Rifluoroacetamide, trimethylsilyltrifluoromethanesulfonate, 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane, trimethylsilylacetylene, hexamethyldisilane, 3-isocyanatopropyltriethoxysilane, tetraisocyanatesilane, methyltri Isocyanate silane, vinyl triisocyanate silane.

Next, the components contained in the toner will be described.
The toner particles having an organosilicon polymer on the surface contain a binder resin, a release agent, and, if necessary, a colorant and other components.
As the binder resin, a resin that is generally used as a binder resin for toner (preferably amorphous) can be used. Specifically, styrene acrylic resins (styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, etc.), polyesters, epoxy resins, styrene-butadiene copolymers, and the like can be used.

It does not specifically limit as a coloring agent, The well-known thing shown below can be used.
Examples of yellow pigments include yellow iron oxide, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.
Examples of the orange pigment include the following. Permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK.

Red pigments include Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake Red D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, etc. Examples include azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254.
Blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, indanthrene blue BG and other copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dyes Examples include lake compounds. Specific examples include the following. C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

Examples of purple pigments include fast violet B and methyl violet lake.
Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite, magnetite, the above-described yellow colorant, red colorant, and blue colorant, and those that are toned in black. These colorants can be used alone or in combination, and further in a solid solution state.
In addition, it is preferable that content of a coloring agent is 3.0 mass part or more and 15.0 mass parts or less with respect to 100 mass parts of polymerizable monomers which produce | generate binder resin or a binder resin.

It does not specifically limit as a mold release agent, The well-known thing shown below can be used.
Petroleum wax such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to Fischer-Tropsch method, polyolefin wax and derivatives thereof such as polyethylene and polypropylene, carnauba wax, Natural waxes such as candelilla wax and derivatives thereof, higher fatty alcohols, fatty acids such as stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes , Animal waxes, silicone resins. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. These can be used alone or in combination.
The content of the release agent is preferably 5.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer that generates the binder resin.

  The toner particles may contain a charge control agent, and known toner particles can be used. The addition amount of these charge control agents is preferably 0.01 to 10.00 parts by mass with respect to 100 parts by mass of the binder resin or the polymerizable monomer that produces the binder resin.

Various organic or inorganic fine powders may be externally added to the toner particles as necessary. The organic or inorganic fine powder preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles in view of durability when added to the toner particles.
As organic or inorganic fine powder, the following are used, for example.
(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black, and carbon fluoride.
(2) Abrasive: metal oxide (for example, strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (for example, silicon nitride), carbide (for example, silicon carbide), metal salt (for example, calcium sulfate, sulfuric acid) Barium, calcium carbonate).
(3) Lubricant: fluororesin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
(4) Charge controllable particles: metal oxide (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

  The surface of the organic or inorganic fine powder may be subjected to a hydrophobic treatment in order to improve the fluidity of the toner and to make the toner particles uniformly charged. As treatment agents for hydrophobic treatment of organic or inorganic fine powders, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, An organic titanium compound is mentioned. These treatment agents may be used alone or in combination.

Hereinafter, specific methods for producing the toner will be described, but the present invention is not limited thereto.
In the first production method, toner particles are obtained by forming toner silicon particles and forming a surface layer of an organosilicon polymer in an aqueous medium. This method is preferable because the organosilicon compound is deposited / polymerized in the vicinity of the surface of the toner base particles, and thus a layer containing the organosilicon polymer can be efficiently formed on the toner particle surface.
That is, toner base particles containing a binder resin are prepared and dispersed in an aqueous medium to obtain a base particle dispersion in which the toner base particles are dispersed. It is preferable to disperse | distribute with the density | concentration from which solid content of a base particle becomes 10 to 40 mass% with respect to the total amount of a base particle dispersion. Further, the temperature of the base particle dispersion is preferably adjusted to 35 ° C. or higher. Furthermore, the pH of the base particle dispersion is adjusted to a pH at which the condensation of the organosilicon compound does not proceed easily. Since the pH at which the condensation of the organosilicon compound is difficult to proceed differs depending on the substance, it is preferably within ± 0.5, centering on the pH at which the reaction is most difficult to proceed.
Next, it is preferable to use a hydrolyzed organosilicon compound. For example, the organosilicon compound is hydrolyzed in a separate container. The preparation concentration of hydrolysis is preferably 40 parts by mass or more and 500 parts by mass or less, more preferably 100 parts by mass of water from which ion content such as ion-exchanged water or RO water is removed when the amount of the organosilicon compound is 100 parts by mass. The amount is 400 parts by mass or less. As the conditions for the hydrolysis, preferably, the pH is 1.0 to 7.0, the temperature is 15 to 80 ° C., and the time is 1 to 600 minutes.
Then, the hydrolyzed organosilicon compound is added to the base particle dispersion. The matrix particle dispersion and the organosilicon compound hydrolyzate are mixed with stirring, and are preferably maintained at 35 ° C. or more and 3 minutes or more and 120 minutes or less. Then, the pH is adjusted to a pH suitable for condensation (preferably pH 6.0 or more and 3.0 or less, more preferably pH 8.0 or more) to condense the organosilicon compound at once, preferably at 35 ° C. or more for 60 minutes or more. The surface layer may be held to form a surface layer containing an organosilicon polymer on the surface of the toner particles.

An example of a method for producing toner base particles will be described below.
(1) Suspension polymerization method: Granulating a polymerizable monomer composition containing a polymerizable monomer capable of forming a binder resin, a release agent, and, if necessary, a colorant in an aqueous medium. Then, toner base particles are obtained by polymerizing the polymerizable monomer.
(2) Crushing method: Toner base particles are obtained by melt-kneading and pulverizing a binder resin, a release agent, and a colorant as required.
(3) Dissolution suspension method: An organic phase dispersion prepared by dissolving a binder resin, a release agent, and, if necessary, a colorant in an organic solvent, is suspended in an aqueous medium, granulated, The toner base particles are obtained by removing the organic solvent after the polymerization.
(4) Emulsion aggregation polymerization method: Toner base particles are obtained by aggregating and associating binder resin particles, release agent particles, and, if necessary, particles such as a colorant in an aqueous medium.

In the second production method, a polymerizable monomer composition containing a polymerizable monomer capable of forming a binder resin, an organosilicon compound, a release agent, and, if necessary, a colorant is contained in an aqueous medium. In this method, toner particles are obtained by granulating and polymerizing the polymerizable monomer.
As a third production method, an organic phase dispersion prepared by dissolving / dispersing a binder resin, an organosilicon compound, a release agent, and, if necessary, a colorant in an organic solvent is suspended in an aqueous medium. In this method, toner particles are obtained by removing the organic solvent after granulation and polymerization.

The fourth production method is a method in which binder resin particles, sol or gel-containing organosilicon compound-containing particles, and if necessary, colorant particles are aggregated in an aqueous medium and associated to form toner particles. .
As the fifth production method, a solvent having an organosilicon compound on the surface of the toner base particles is sprayed onto the surface of the toner base particles by a spray drying method, and the surface is polymerized or dried by hot air and cooling to obtain a surface layer containing an organosilicon compound. It is a method of forming.
In addition, as an aqueous medium, the following are mentioned. Water; a mixed solvent of water and alcohols such as methanol, ethanol, and propanol;

As a method for producing toner particles, among the production methods described above, the method of producing toner base particles by suspension polymerization among the first production methods is most preferable. In the suspension polymerization method, the organosilicon polymer is likely to be uniformly deposited on the surface of the toner particles, and the environmental stability, the development transferability, and the durability durability thereof are improved. Hereinafter, the suspension polymerization method will be further described.
You may add another resin to the said polymerizable monomer composition as needed. After completion of the polymerization step, the produced particles are collected by washing and filtration, and dried to obtain toner base particles. The temperature may be raised in the latter half of the polymerization step. Furthermore, in order to remove the unreacted polymerizable monomer or by-product, it is possible to partially distill off the dispersion medium from the reaction system in the latter half of the polymerization step or after the completion of the polymerization step. Note that the surface layer containing the organosilicon polymer may be formed using a base particle dispersion in which the toner base particles are dispersed without performing washing, filtration and drying after the polymerization step.

As the above-mentioned other resins, the following resins can be used as long as the effects of the present invention are not affected.
Styrene such as polystyrene and polyvinyltoluene, and homopolymers of substituted styrene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene -Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethyl methacrylate ethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Coalescence, styrene-pig Styrene copolymers such as ene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene , Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These can be used alone or in combination.

Preferred examples of the polymerizable monomer in the suspension polymerization method include the following vinyl polymerizable monomers. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate , Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, Acrylic polymerizable monomers such as n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl Methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2
-Methacrylic polymerizable monomers such as ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, propionic acid Vinyl esters such as vinyl, vinyl benzoate, vinyl butyrate and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.
Among these monomers, styrene, styrene derivatives, acrylic polymerizable monomers, and methacrylic polymerizable monomers are preferable.

Further, a polymerization initiator may be added during the polymerization of the polymerizable monomer. The following are mentioned as a polymerization initiator. 2,2′-azobis- (2,4-divaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo-type or diazo-type polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 30.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and may be used alone or in combination.
In order to control the molecular weight of the binder resin constituting the toner particles, a chain transfer agent may be added during the polymerization of the polymerizable monomer. A preferable addition amount is 0.001 to 15,000 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

In order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization of the polymerizable monomer. The following are mentioned as a crosslinkable monomer. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates replaced with methacrylate of.
The following are mentioned as a polyfunctional crosslinking monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate. A preferable addition amount is 0.001 to 15,000 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

When the medium used in the suspension polymerization is an aqueous medium, the following can be used as the dispersion stabilizer for the particles of the polymerizable monomer composition. Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina .
Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose,
Sodium salt of carboxymethyl cellulose, starch.
Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

Hereinafter, various measurement methods related to the present invention will be described.
In the case where an organic fine powder or an inorganic fine powder is externally added to the toner, a sample obtained by removing the organic fine powder or the inorganic fine powder by the following method or the like is used as a sample.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water, and dissolved with a hot water bath to prepare a sucrose concentrate. In a centrifuge tube (capacity: 50 ml), 31 g of the above sucrose concentrate and Contaminone N (neutral detergent for pH7 precision measuring instrument washing consisting of nonionic surfactant, anionic surfactant and organic builder) 6 mL of 10 mass% aqueous solution (made by Wako Pure Chemical Industries Ltd.) is put. To this, 1.0 g of toner is added, and a lump of toner is loosened with a spatula or the like. The centrifuge tube is shaken with a shaker (sold from AS-1N ASONE Co., Ltd.) at 300 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for swing rotor (50 mL) and separated by a centrifuge (H-9R manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes.
By this operation, the toner particles and the external additive are separated. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the toner separated in the uppermost layer is collected with a spatula or the like. The collected toner is filtered with a vacuum filter and then dried with a dryer for 1 hour or longer to obtain a measurement sample. Perform this operation multiple times to ensure the required amount.

<Acquisition method of reflected electron image on toner particle surface>
The reflected electron image on the surface of the toner particles was obtained with a scanning electron microscope (SEM).
The SEM apparatus and observation conditions are as follows.
Equipment used: ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd.
Acceleration voltage: 1.0 kV
WD: 2.0mm
Aperture Size: 30.0 μm
Detection signal: EsB (energy selective reflected electrons)
EsB Grid: 800V
Observation magnification: 50,000 times Contrast: 63.0 ± 5.0% (reference value)
Brightness: 38.0 ± 5.0% (reference value)
Resolution: 1024 x 768
Pretreatment: Scatter toner particles on carbon tape (no vapor deposition)
The contrast and brightness are determined according to the following procedure. First, the contrast is set so that the two maximum values P1 and P2 have the largest possible number of pixels on the luminance histogram, and the luminances of P1 and P2 are separated as much as possible. Next, the brightness is set so that the bottoms of the two peaks having the maximum values P1 and P2 are within the luminance histogram. These contrast and brightness are appropriately set according to the procedure according to the state of the device used. The acceleration voltage and EsB Grid of the present invention are set so as to achieve items such as acquisition of structural information on the outermost surface of toner particles, prevention of charge-up of an undeposited sample, and selective detection of high-energy reflected electrons. . The observation visual field is selected near the apex where the curvature of the toner particles is the smallest.

<Method for confirming that P2 is derived from an organosilicon polymer>
It was confirmed that P2 was derived from an organosilicon polymer by superimposing an element mapping image obtained by energy dispersive X-ray analysis (EDS) that can be obtained with a scanning electron microscope (SEM) and the reflected electron image.
The SEM / EDS apparatus and observation conditions are as follows.
Device used (SEM): ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd.
Equipment used (EDS): Thermo Fisher Scientific Co., Ltd., NORANSystem 7, Ultra Dry EDS Detector
Acceleration voltage: 5.0 kV
WD: 7.0mm
Aperture Size: 30.0 μm
Detection signal: SE2 (secondary electron)
Observation magnification: 50,000 times Mode: Spectral Imaging
Pre-treatment: Scattering toner particles on carbon tape, platinum spattering The mapping image of silicon element obtained by this method and the reflected electron image are superimposed, and the silicon atom part of the mapping image and the bright part of the reflected electron image coincide with each other Make sure you do.

<Luminance histogram acquisition method>
The luminance histogram is obtained by analyzing the reflected electron image on the surface of the toner particles obtained by the above method using image processing software ImageJ (developer Wayne Rand). The procedure is shown below.
First, from the Type of the Image menu, the reflected electron image to be analyzed is converted into 8-bit. Next, the Median diameter is set to 2.0 pixels from Filters in the Process menu, and image noise is reduced. The center of the image is estimated after removing the observation condition display part displayed at the bottom of the backscattered electron image, and a 1.5 μm square range is selected from the center of the backscattered electron image using the rectangular tool (Rectangle Tool) on the toolbar. .
Next, Histgram in the Analyze menu is selected, and a luminance histogram is displayed in a new window. The value of the luminance histogram is acquired from the List of the window. If necessary, luminance histogram fitting may be performed. From this, the luminance and the number of pixels that give the maximum values P1 and P2, the luminance Bl that gives the minimum value V, and the numbers of pixels A1, A2, and AV are calculated.
The above procedure was performed for 10 visual fields for the toner particles to be evaluated, and the average value of each was used as the physical property value of the toner particles obtained from the luminance histogram.

<Analysis of Domain Formed by Pixel Group A (Calculation of Area and Ferret Diameter)>
The domain (particle A1) formed by the pixel group A is analyzed using the image processing software ImageJ (developed by Wayne Randhand) on the surface of the toner particle obtained by the above method. The procedure is shown below.
First, the backscattered electron image is converted into 8-bit from the type of the Image menu. Next, the Median diameter is set to 2.0 pixels from Filters in the Process menu, and image noise is reduced. The center of the image is estimated after removing the observation condition display part displayed at the bottom of the backscattered electron image, and a 1.5 μm square range is selected from the center of the backscattered electron image using the rectangular tool (Rectangle Tool) on the toolbar. .
Next, Threshold is selected from “Adjust” in the Image menu. In the manual operation, all pixels corresponding to a luminance range of 0 or more (Bl-30) or less are selected, and Apply is clicked to obtain a binarized image. By this operation, the pixel corresponding to A1 is displayed in black. Once again, the image center is estimated after removing the observation condition display part displayed at the bottom of the backscattered electron image, and the range of 1.5 μm square from the center of the backscattered electron image is estimated using the rectangle tool (Rectangle Tool) on the toolbar. select.
Next, the scale bar in the observation condition display part displayed under the backscattered electron image is selected using a straight line tool (Stright Line) on the tool bar. In this state, when “Set Scale” is selected from the Analyze menu, a new window is opened, and the pixel distance of the selected straight line is input in the “Distance in Pixels” column. Enter the scale bar value (eg, 100) in the Known Distance column of the window, enter the scale bar unit (eg, nm) in the Unit of Measurement column, and click OK to complete the scale setting. Next, select Set Measurements from the Analyze menu, and check Area and Feret's diameter. Select “Analyze Particles” in the “Analyze” menu, check “Display Result” and click “OK” to perform particle analysis. From the newly opened Results window, the particle area (Area) and the particle ferret diameter (Feret) for each particle corresponding to the domain (particle A1) formed by the pixel group A are acquired, and the number average value is calculated.
The above procedure is performed for 10 visual fields for the toner particles to be evaluated, and the respective arithmetic mean values are used.

<Method for confirming network structure of organosilicon polymer>
The organic silicon polymer on the toner particle surface has a network structure in which particles composed of pixels having a luminance range of 0 or more (Bl-30) or less on the toner particle surface (pixel group A is a mesh) The formation of a network structure by the pixel group B was confirmed by the following method.
In the same manner as the particle analysis method for the domain (particle A1) formed by the pixel group A, a 1.5 μm square binarized image in which a pixel portion having a luminance range of 0 to (Bl-30) is black is obtained. . At that time, if it has a shape as shown in FIG. 2 (a ′), it is determined that the organosilicon polymer forms a network structure.

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. Measured data with 25,000 effective measurement channels using the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for condition setting and measurement data analysis It was calculated by performing the analysis.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows. In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked. In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) About 200 mL of the electrolytic solution is placed in a glass 250 mL round-bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture tube flush” function of the dedicated software.
(2) About 30 mL of the electrolytic aqueous solution is put in a glass 100 mL flat-bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder consisting of an organic builder) is used as a dispersant. About 0.3 mL of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water three times as much is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W A predetermined amount of ion-exchanged water is added, and about 2 mL of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolytic solution (5) in which the toner particles are dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Method for confirming structure represented by formula (RaT3)>
The structure represented by the formula (RaT3) of the organosilicon polymer is confirmed using a nuclear magnetic resonance apparatus (NMR).
The sample for NMR measurement is prepared as follows.
Preparation of measurement sample: 10.0 g of toner particles are weighed, placed in a cylindrical filter paper (No. 86R manufactured by Toyo Roshi), passed through a Soxhlet extractor, extracted with 200 ml of tetrahydrofuran as a solvent for 20 hours, and the filtrate in the cylindrical filter paper. The sample obtained by vacuum drying at 40 ° C. for several hours is used as a sample for NMR measurement.

Of the structure represented by the formula (RaT3), Ra bonded to the silicon atom is confirmed by ¹³ C-NMR (solid) measurement. The measurement conditions are shown below.
"Measurement conditions for ¹³ C-NMR (solid)"
Apparatus: JNM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran insoluble in toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP / MAS
Measurement nuclear frequency: 123.25 MHz ( ¹³ C)
Reference substance: adamantane (external standard: 29.5 ppm)
Sample rotation speed: 20 kHz
Contact time: 2ms
Delay time: 2s
Cumulative number: 1024 times In the formula (RaT3), when Ra is a structure represented by a hydrocarbon group having 1 to 6 carbon atoms, a methyl group (Si—CH ₃ ), an ethyl group ( _{Si-C 2 H} 5), propyl _{(Si-C 3 H 7)} , butyl group _{(Si-C 4 H 9)} , a pentyl group _{(Si-C 5 H 11)} , a hexyl group _{(Si-C 6 H 13} ), A phenyl group (Si—C ₆ H ₅ )) and the like, and the presence of Ra is confirmed.
In the formula (RaT3), in the case where Ra is a structure represented by the formula (i), the presence or absence of a signal due to a methine group bonded to a silicon atom (> CH—Si) Confirm the existence of the structure represented.
In the case where Ra is a structure represented by the formula (ii), an alkylene group or arylene such as a methylene group (Si—CH ₂ —) or an ethylene group (Si—C ₂ H ₄ —) bonded to a silicon atom The presence of the structure represented by formula (ii) is confirmed by the presence or absence of a signal due to a group (for example, a phenylene group (Si—C ₆ H ₄ —)) or the like.

Of the structure represented by the formula (RaT3), the siloxane bond portion was confirmed by ²⁹ Si-NMR (solid) measurement. The measurement conditions are shown below.
"Measurement conditions for ²⁹ Si-NMR (solid)"
Apparatus: JNM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran insoluble in toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP / MAS
Measurement nuclear frequency: 97.38 MHz ( ²⁹ Si)
Reference substance: DSS (external standard: 1.534 ppm)
Sample rotation speed: 10 kHz
Contact time: 10ms
Delay time: 2s
Accumulated number: 2000 to 8000 times After the above measurement, the following X1 structure, X2 structure, X3 structure, and X4 structure are obtained by curve fitting with a plurality of silane components having different substituents and bonding groups in the tetrahydrofuran-insoluble portion of the toner particles. Separate the peaks and calculate the peak areas.
X1 structure represented by formula (5): (Ri) (Rj) (Rk) SiO _1/2
X2 structure represented by formula (6): (Rg) (Rh) Si (O _1/2 ) ₂
X3 structure represented by formula (7): RmSi (O _1/2 ) ₃
X4 structure represented by formula (8): Si (O _1/2 ) ₄

(In the formulas (5) to (8), Ri, Rj, Rk, Rg, Rh, Rm are organic groups such as hydrocarbon groups having 1 to 6 carbon atoms bonded to silicon atoms, halogen atoms, hydroxy A group, an acetoxy group or an alkoxy group.)
In the formulas (5) to (8), the structures of the portions surrounded by the rectangle are the X1 structure to the X4 structure, respectively.
In the chart obtained by ²⁹ Si-NMR measurement of the tetrahydrofuran insoluble matter of the toner, the ratio of the peak area attributed to the structure of the formula (RaT3) to the total peak area of the organosilicon polymer is 20% or more and 100% or less. It is preferable that it is 40% or more and 80% or less.
Incidentally, when it is necessary to confirm the structure of formula (RaT3) in more detail, it may be identified by measurement results of ¹ H-NMR together with the measurement results of the ¹³ C-NMR and ²⁹ Si-NMR.

  Hereinafter, the present invention will be described in more detail with reference to specific production examples, examples, and comparative examples, but this does not limit the present invention in any way. The “part” in the following prescription is based on mass unless otherwise specified.

[Production Example of Toner 1]
<Preparation process of aqueous medium 1>
To 1000.0 parts of ion-exchanged water in the reaction vessel, 14.0 parts of sodium phosphate (manufactured by Lhasa Kogyo Co., Ltd., 12 hydrate) was added and kept at 65 ° C. for 1.0 hour while purging with nitrogen. T.A. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), aggregating aqueous calcium chloride solution containing 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water while stirring at 12,000 rpm. The aqueous medium containing the dispersion stabilizer was prepared. Further, 10% by mass hydrochloric acid was added to the aqueous medium, and the pH was adjusted to 6.0, whereby an aqueous medium 1 was obtained.

<Preparation process of polymerizable monomer composition>
-Styrene: 60.0 parts-C.I. I. Pigment Blue 15: 3: 6.5 parts The above material was put into an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.), and further dispersed using a zirconia particle having a diameter of 1.7 mm at 220 rpm for 5.0 hours. A dispersion was prepared. The following materials were added to the pigment dispersion.
-Styrene: 14.0 parts-n-Butyl acrylate: 26.0 parts-Crosslinking agent (divinylbenzene): 0.2 parts-Saturated polyester resin: 6.0 parts (Propylene oxide-modified bisphenol A (2 mol adduct)) And terephthalic acid polycondensate (molar ratio 10:12), glass transition temperature Tg = 68 ° C., weight average molecular weight Mw = 10000, molecular weight distribution Mw / Mn = 5.12)
Fischer-Tropsch wax (melting point 78 ° C.): 10.0 parts Charge control agent: 0.5 parts (aluminum compound of 3,5-di-tert-butylsalicylic acid)
This was kept at 65 ° C. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the solution was uniformly dissolved and dispersed at 500 rpm to prepare a polymerizable monomer composition.

<Preparation process of organosilicon compound aqueous solution>
In a reaction vessel equipped with a stirrer and a thermometer, 60.0 parts of ion-exchanged water was weighed and the pH was adjusted to 1.5 using 10% by mass hydrochloric acid. This was heated with stirring to bring the temperature to 60 ° C. Thereafter, 40.0 parts of methyltriethoxysilane was added and stirred for 2 minutes to obtain an organic silicon compound aqueous solution 1.

<Granulation process>
While maintaining the temperature of the aqueous medium 1 at 70 ° C. and the rotational speed of the stirrer at 12000 rpm, the polymerizable monomer composition was introduced into the aqueous medium 1 and t-butyl peroxypivalate as a polymerization initiator 9. 0 parts were added. The mixture was granulated for 10 minutes while maintaining 12000 rpm with the stirring device.

<Polymerization process>
The stirrer is changed from a high-speed stirrer to a propeller stirring blade, polymerization is performed for 5.0 hours while maintaining at 70 ° C. while stirring at 150 rpm, and the polymerization reaction is performed by heating to 95 ° C. and heating for 2.0 hours. And a slurry of toner particles was obtained. Then, when the temperature of the slurry was cooled to 60 ° C. and the pH was measured, it was pH = 5.0. While continuing stirring at 60 ° C., 20.0 parts of the organosilicon compound aqueous solution 1 was added. After maintaining for 30 minutes, the slurry was adjusted to pH = 9.0 using an aqueous sodium hydroxide solution and further maintained for 300 minutes to form an organosilicon polymer on the surface of the toner particles.

<Washing and drying process>
After completion of the polymerization process, the toner particle slurry is cooled, hydrochloric acid is added to the toner particle slurry, the pH is adjusted to 1.5 or lower, and the mixture is left to stir for 1 hour, and then solid-liquid separated with a pressure filter, and the toner cake Got. This was reslurried with ion-exchanged water to obtain a dispersion again, followed by solid-liquid separation with the above-mentioned filter. Reslurry and solid-liquid separation were repeated until the electric conductivity of the filtrate was 5.0 μS / cm or less, and finally solid-liquid separation was performed to obtain a toner cake.
The obtained toner cake was dried with an air-flow dryer flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and fine particles were cut using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1.
The drying conditions were adjusted such that the blowing temperature was 90 ° C., the dryer outlet temperature was 40 ° C., and the supply speed of the toner cake was adjusted so that the outlet temperature did not deviate from 40 ° C. according to the moisture content of the toner cake. In this example, the obtained toner particles 1 were used as toner 1 as they were without external addition. It was confirmed by the above-described method that the toner 1 has a surface layer containing an organosilicon polymer on the toner particle surface. Table 2 shows the physical properties of the obtained toner.

[Production Examples of Toner 2-19, Comparative Toners 1, 2, 5, 6]
According to the formulation and production conditions shown in Table 1, toners 2 to 19 and comparative toners 1, 2, 5, and 6 were obtained in the same manner as in the above toner 1 production example. Table 2 shows the physical properties of the obtained toner.

[Production Example of Comparative Toner 3]
In the production example of toner 1, in the preparation step of the polymerizable monomer composition, 12.0 parts of methyltriethoxysilane was added as a monomer to the pigment dispersion. The preparation process of the organosilicon compound aqueous solution was not performed. The hydrolysis solution was not added in the polymerization step, and only pH adjustment and subsequent holding were performed. Other than that, Comparative toner 3 was produced in the same manner as in the toner 1 production example. Table 2 shows the physical properties of the obtained toner.

[Production Example of Comparative Toner 4]
Comparative toner 4 was obtained in the same manner as in comparative toner 3 except that the number of parts of methyltriethoxysilane was changed to 7.4 parts in the comparative toner 3 manufacturing example. Table 2 shows the physical properties of the obtained toner.

[Production Example of Comparative Toner 7]
In the production example of the toner 1, the organic silicon compound aqueous solution preparation process was not performed. After obtaining a slurry of toner particles in the polymerization step, 8.0 parts of methyltriethoxysilane was added as a monomer while the temperature of the slurry was cooled to 60 ° C. and stirring was continued. After maintaining for 30 minutes, the slurry was adjusted to pH = 9.0 using an aqueous sodium hydroxide solution and further maintained for 300 minutes to form an organosilicon polymer on the surface of the toner particles. Other than that, Comparative toner 7 was produced in the same manner as in the toner 1 production example. Table 2 shows the physical properties of the obtained toner.

[Production Example of Comparative Toner 8]
Comparative toner 8 was obtained in the same manner as in Comparative toner 7 except that the number of parts of methyltriethoxysilane was changed to 9.4 parts. Table 2 shows the physical properties of the obtained toner.

[Production Example of Comparative Toner 9]
In the production example of the toner 1, the organic silicon compound aqueous solution preparation process was not performed. After obtaining a slurry of toner particles in the polymerization step, 250 parts of methyltriethoxysilane was added as a monomer while the temperature of the slurry was cooled to 25 ° C. and stirring was continued. Further, 4000.0 parts of ion exchange water was added. After holding this solution for 30 minutes, p
The solution was added dropwise to 10000.0 parts of an aqueous sodium hydroxide solution adjusted to H = 9.0, and held at 25 ° C. for 48 hours to form an organosilicon polymer on the toner particle surface. Other than that, Comparative Toner 9 was produced in the same manner as in Toner 1 Production Example. Table 2 shows the physical properties of the obtained toner.

[Image output evaluation]
<Evaluation of winding property at low temperature fixing>
The fixing unit of the Canon laser beam printer LBP9600C was modified so that the fixing temperature could be adjusted. Using this modified LBP9600C, the fixing temperature was changed from 140 ° C. in increments of 5 ° C. in a normal speed (25 ° C./50% RH) environment at a process speed of 300 mm / sec. For the toner to be evaluated, a solid image having a toner loading of 0.40 mg / cm ² was formed on the image receiving paper, and heated and pressurized oillessly to form a fixed image on the image receiving paper. At this time, the state of the paper passing was visually confirmed, the temperature of the fixing device when the paper was passed without winding was examined, and the winding property at low temperature fixing was evaluated based on the following criteria. As the image receiving paper, GF-600 (amount of 60 g / m ² , sold from Canon Marketing Japan Inc.) was used.
A: Less than 150 ° C. B: 150 ° C. or more and less than 155 ° C. C: 155 ° C. or more and less than 160 ° C. D: 160 ° C. or more and less than 170 ° C. E: 170 ° C. or more In the present invention, C or more was judged good.

<Evaluation of transfer boss>
A tandem Canon laser beam printer LBP9600C having the configuration as shown in FIG. 3 was modified to enable printing only with the cyan station. A toner cartridge for LBP9600C was filled with 200 g of the toner to be evaluated, and the toner cartridge was left in a high temperature and high humidity (32.5 ° C./85% RH) environment for 24 hours.
The toner cartridge left for 24 hours was attached to the LBP 9600C, and an image with a printing ratio of 1.0% was printed out to 15,000 sheets in the A4 paper lateral direction. After outputting 15,000 sheets, a solid image with a toner loading of 0.40 mg / cm ^{2 was} output to CS-680 (basis weight 68 g / m ² , sold by Canon Marketing Japan Inc.). This image was visually observed, and the transfer edge was evaluated based on the following criteria. In the present invention, the portion where the image uniformity is impaired is determined to be a transfer edge.
The symbols in FIG. 3 are as follows.
1: Photoconductor, 2: Developing roller, 3: Toner supply roller, 4: Toner, 5: Regulating blade, 6: Developing device, 7: Laser beam, 8: Charging device, 9: Cleaning device, 10: Charging for cleaning Device: 11: stirring blade, 12: driving roller, 13: transfer roller, 14: bias power source, 15: tension roller, 16: transfer conveying belt, 17: driven roller, 18: paper, 19: paper feeding roller, 20: Adsorption roller, 21: Fixing device A: Even if the light is held under normal light or strong light, the transfer edge cannot be seen. B: When the light is held under normal light, the transfer edge is not seen. C: A transfer bulge is observed C: One or two transfer bulges are seen even under normal light, but no white spots are observed D: Three or four transcribed transfer blebs are seen even under normal light, but white There is no missing E: Normal light But, more than five points transfer tailed seen, or one place or more white spots in the present invention is seen was judged to be good or more C.

<Evaluation of low-temperature fixability>
Similar to the evaluation of wrapping property at low temperature fixing, using LBP9600C modified so that the fixing temperature can be adjusted, at a process speed of 300 mm / sec, at normal temperature and humidity (25 ° C./50% R
H) The fixing temperature was changed from 140 ° C. in increments of 5 ° C. under the environment. For the toner to be evaluated, a solid image having a toner loading of 0.40 mg / cm ² was formed on the image receiving paper, and heated and pressurized oillessly to form a fixed image on the image receiving paper. Using Kimwipe (S-200, manufactured by Crecia Co., Ltd.), the fixed image was rubbed 10 times with a load of 75 g / cm ² , and the temperature at which the image density reduction rate before and after rubbing was less than 5% was defined as the fixing temperature. Evaluation based on the criteria of.
As the image receiving paper, business 4200 (a weight of 105 g / m ² , manufactured by Xerox) was used. For the measurement of the image density, a color reflection densitometer X-RITE 404A (manufactured by X-Rite Co.) is used to measure the relative density with respect to the printout image of the white background portion where the document density is 0.00, and the image density after rubbing. The reduction rate was calculated.
A: Less than 150 ° C. B: 150 ° C. or more and less than 160 ° C. C: 160 ° C. or more and less than 170 ° C. D: 170 ° C. or more In the present invention, C or more was judged to be good.

[Examples 1-19, Comparative Examples 1-8]
Each toner shown in Tables 1 and 2 was evaluated for winding property at low temperature fixing, transfer margin, and low temperature fixing property. The results are shown in Table 3.

1: Photoconductor, 2: Developing roller, 3: Toner supply roller, 4: Toner, 5: Regulating blade, 6: Developing device, 7: Laser beam, 8: Charging device, 9: Cleaning device, 10: Charging for cleaning Device: 11: stirring blade, 12: driving roller, 13: transfer roller, 14: bias power source, 15: tension roller, 16: transfer conveying belt, 17: driven roller, 18: paper, 19: paper feeding roller, 20: Adsorption roller, 21: fixing device

Claims (3)

A toner having toner particles having a binder resin and a release agent,
The toner particles have a surface layer containing an organosilicon polymer,
In the scanning electron microscope observation of the surface of the toner particle, a reflected electron image of 1.5 μm square on the surface of the toner particle is obtained, and the luminance of each pixel constituting the reflected electron image is 256 gradations from luminance 0 to luminance 255. And obtaining a luminance histogram with the horizontal axis representing the luminance and the vertical axis representing the number of pixels,
(I) There are two maximum values P1 and P2 and a minimum value V between P1 and P2, and the peak containing P2 is a peak derived from the organosilicon polymer,
(Ii) The luminance giving P1 is 20 or more and 70 or less,
(Iii) The luminance giving P2 is 130 or more and 230 or less,
(Iv) The ratio of P1 and P2 to the total number of pixels of the reflected electron image is 0.50% or more,
(V) The luminance giving V is B1, the total number of pixels in the luminance range 0 to (Bl-30) is A1, the total number of pixels in the luminance range (Bl-29) to (Bl + 29) is AV, the luminance range ( B1 + 30) to 255, where A2 is the total number of pixels, the following formulas (1) and (2)
(A1 / AV) ≧ 1.50 (1)
(A2 / AV) ≧ 1.50 (2)
Meet,
Toner characterized by the above. The organosilicon polymer forms a network structure on the toner particle surface,
In the reflected electron image, when all the pixels are divided into a pixel group A having a luminance range of 0 or more (Bl-30) and a pixel group B having a luminance range (Bl-29) or more and 255 or less, the pixel group A And a network structure by the pixel group B is observed,
The domain formed by the pixel group A is
(I) The number average value of the area is 2.00 × 10 ³ nm ² or more and 1.00 × 10 ⁴ nm ² or less,
(Ii) The number average value of the particle ferret diameter is 60 nm or more and 200 nm or less.
The toner according to claim 1. The toner according to claim 1, wherein the organosilicon polymer is a polymer having a structure represented by the following formula (RaT3).
[In the formula, Ra represents a hydrocarbon group having 1 to 6 carbon atoms, or a vinyl polymer moiety including a partial structure represented by the following formula (i) or the following formula (ii). In the formulas (i) and (ii), * represents a bonding site with the Si element in the structure represented by the formula (RaT3), and L in the formula (ii) represents an alkylene group or an arylene group. ]

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