JP7140543B2 - toner - Google Patents

Description

The present invention relates to toners for developing electrostatic images used in imaging processes 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 demand, various studies have been made to develop a toner excellent in low-temperature fixability and development transferability.
Among them, there has been proposed a toner that maintains low-temperature fixability and prevents thin paper from being wound around a heating member of a fixing device. Patent Literature 1 discloses a technique for suppressing winding by coating a core particle with a resin shell layer and forming certain holes in the shell layer. However, the use of only a resin shell layer poses a problem in terms of development transferability from the viewpoint of fluidity and chargeability, so an external additive is required. On the other hand, there is still room for improvement in terms of durability, because external additives become embedded and come off as a result of continuous use.
In view of this, Patent Document 2 proposes a toner having both a coating layer of a silane compound and externally added inorganic particles as a technique for enhancing charging stability and improving durability.

JP 2009-186640 A Japanese Patent No. 5407377

However, in the technique described in Patent Document 2, fixability inhibition due to high coverage of the toner base particles cannot be ignored, and there remains a problem of thin paper winding around the fixing device, especially at low temperatures. rice field.
An object of the present invention is to provide a toner that achieves both low-temperature fixability and development transferability after continuous use. To provide a toner which hardly causes transfer dust even later.

［式（ＲａＴ３）中、Ｒａは、炭素数が１以上６以下の炭化水素基を表す。］
該トナー粒子の表面の走査電子顕微鏡観察において、該トナー粒子の表面１．５μｍ四方の反射電子像を取得し、該反射電子像を構成する各ピクセルの輝度を輝度０から輝度２５５の２５６階調に振り分けて、横軸を輝度、縦軸をピクセル数とする輝度ヒストグラムを得たとき、該輝度ヒストグラムにおいて、
（ｉ）二つの極大値Ｐ１及びＰ２と、該Ｐ１及び該Ｐ２間の極小値Ｖが存在し、該Ｐ２を含むピークは、該有機ケイ素重合体に由来するピークであり、
（ｉｉ）該Ｐ１を与える輝度が２０以上７０以下であり、
（ｉｉｉ）該Ｐ２を与える輝度が１３０以上２３０以下であり、
（ｉｖ）該反射電子像の全ピクセル数に対する該Ｐ１及び該Ｐ２の割合が、それぞれ０．５０％以上であり、
（ｖ）該Ｖを与える輝度をＢｌとし、輝度範囲０以上（Ｂｌ－３０）以下における合計ピクセル数をＡ１とし、輝度範囲（Ｂｌ－２９）以上（Ｂｌ＋２９）以下における合計ピクセル数をＡＶとし、輝度範囲（Ｂｌ＋３０）以上２５５以下における合計ピクセル数をＡ２としたとき、下記式（１）及び（２）
（Ａ１／ＡＶ）≧１．５０ （１）
（Ａ２／ＡＶ）≧１．５０ （２）
を満たす、
ことを特徴とするトナーに関する。 The present invention provides a toner having toner particles having a binder resin and a release agent,
The toner particles have a surface layer containing an organosilicon polymer,
The organosilicon polymer is a polymer having a structure represented by the following formula (RaT3),

[In the formula (RaT3), Ra represents a hydrocarbon group having 1 to 6 carbon atoms. ]
In scanning electron microscope observation of the surface of the toner particles, a backscattered electron image of 1.5 μm square of the surface of the toner particles is obtained, and the brightness of each pixel constituting the backscattered electron image is adjusted to 256 gradations from brightness 0 to brightness 255. to obtain a luminance histogram with the horizontal axis as the luminance and the vertical axis as the number of pixels, in the luminance histogram,
(i) there are two maximum values P1 and P2 and a minimum value V between the P1 and the P2, and the peak containing the P2 is a peak derived from the organosilicon polymer;
(ii) the luminance that gives the P1 is 20 or more and 70 or less;
(iii) the luminance that gives the P2 is 130 or more and 230 or less;
(iv) the ratio of the P1 and the P2 to the total number of pixels of the backscattered electron image is 0.50% or more;
(v) let Bl be the luminance that gives the V, let A1 be the total number of pixels in the luminance range of 0 or more (Bl-30) or less, and let AV be the total number of pixels in the luminance range of (Bl-29) or more (Bl+29) or less; When the total number of pixels in the luminance range (Bl + 30) or more and 255 or less is A2, the following formulas (1) and (2)
(A1/AV)≧1.50 (1)
(A2/AV)≧1.50 (2)
satisfy the
The present invention relates to a toner characterized by:

According to the present invention, it is possible to provide a toner in which thin paper is less likely to be wrapped around a fixing device during low-temperature fixing and less likely to cause transfer dust even after endurance in a high-temperature and high-humidity environment.

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

In the present invention, unless otherwise specified, the descriptions of "○○ or more and XX or less" and "○○ to XX", which represent numerical ranges, mean numerical ranges including the lower and upper limits that are endpoints.
The present invention will be described in detail below.
The present invention provides 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 scanning electron microscope observation of the surface of the toner particles, a backscattered electron image of 1.5 μm square of the surface of the toner particles is obtained, and the brightness of each pixel constituting the backscattered electron image is adjusted to 256 gradations from brightness 0 to brightness 255. to obtain a luminance histogram with the horizontal axis as the luminance and the vertical axis as the number of pixels, in the luminance histogram,
(i) there are two maximum values P1 and P2 and a minimum value V between the P1 and P2, and the peak containing the P2 is a peak derived from the organosilicon polymer;
(ii) the luminance that gives the P1 is 20 or more and 70 or less;
(iii) the luminance that gives the P2 is 130 or more and 230 or less;
(iv) the ratio of the P1 and the P2 to the total number of pixels of the backscattered electron image is 0.50% or more;
(v) Bl is the luminance that gives the V, A1 is the total number of pixels in the luminance range 0 or more (Bl-30) or less, AV is the total number of pixels in the luminance range (Bl-29) or more (Bl + 29) or less, and the luminance range ( Bl + 30) or more and 255 or less, when the total number of pixels is A2, the following formulas (1) and (2)
(A1/AV)≧1.50 (1)
(A2/AV)≧1.50 (2)
satisfy the
It is characterized by

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

Here, the base refers to a composition containing carbon as a main component, such as a binder resin and a releasing agent, contained in the toner particles. In addition, it can be confirmed that the peak containing P2 is derived from the organosilicon polymer by superimposing the elemental mapping image by energy dispersive X-ray analysis (EDS) obtained by scanning electron microscope observation and the backscattered electron image. . It is one of the requirements of the present invention that such a bimodal histogram having P1 derived from the matrix of the toner particles, P2 derived from the organosilicon polymer, and the minimum value V between P1 and P2 ( For example, FIG. 1(a)). If the luminance histogram is a unimodal histogram that has one maximum value (P1 or P2) and no minimum value V, as shown in FIG. 1(b), it does not meet the requirements of the present invention.

It is also important that the luminance giving P1 is 20 or more and 70 or less and the luminance giving 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, the peak 1 having the maximum value P1 and the peak 2 having the maximum value P2 overlap less and are separated. become good. It should be noted that "brightness giving P1" or "brightness giving P2" means the brightness when the number of pixels takes the maximum value P1 or the maximum value P2, respectively.
As described above, the peak containing P1 is derived from the matrix of the toner particles, and the peak containing P2 is derived from the organosilicon polymer. If the peaks 1 and 2 are well separated, the toner particle base and the organosilicon polymer are efficiently localized on the toner particle surface, and their respective functions described below are more effectively exhibited. It is preferable that the luminance giving P1 is 20 or more and 60 or less, and the luminance giving P2 is 140 or more and 230 or less.

Moreover, it is necessary that the ratio of P1 and P2 to the total number of pixels of the backscattered electron image is 0.50% or more.
Furthermore, Bl is the luminance that gives the minimum value V, A1 is the total number of pixels in the luminance range of 0 or more (Bl-30) or less, AV is the total number of pixels in the luminance range of (Bl-29) or more (Bl+29) or less, and the luminance range ( Bl + 30) or more and 255 or less, when the total number of pixels is A2, the following formulas (1) and (2)
(A1/AV)≧1.50 (1)
(A2/AV)≧1.50 (2)
is an essential requirement (for example, FIG. 1(a)). A luminance histogram as shown in FIG. 1(c), which does not have the relationships of the above formulas (1) and (2), does not satisfy the requirements of the present invention. Here, the number of pixels A1 in the luminance range of 0 or more (Bl-30) or less has the peak 1 with P1 as the maximum value, and the number of pixels A2 in the luminance range of (Bl+30) or more to 255 or less has P2 as the maximum. Peak 2 is the main component. As described above, since P1 is derived from the toner particle base and P2 is derived from the organosilicon polymer, each pixel included in A1 is attributed to the toner particle matrix, and each pixel included in A2 is attributed to the organosilicon polymer. be done.

That is, the larger P1 is, the larger the A1 is, the larger the base component is, and the larger the P2 is, the larger the A2 is, the more the organosilicon polymer component is present on the toner particle surface. As a result, it is possible to achieve a toner in which thin paper is less likely to be wrapped around the fixing device even during low-temperature fixing, and less likely to cause transfer dust even after endurance in a high-temperature and high-humidity environment.
If the matrix component of the toner particles is sufficiently present on the toner particle surface, the release agent tends to seep out from the matrix of the toner particles even when the fixing temperature is low. It is known that thin paper tends to be wrapped around the paper, but an appropriate amount of release agent oozes out from the matrix of the toner particles during fixing, thereby facilitating the separation of the fuser member from the thin paper. The ratio of P1 to the total number of pixels of the backscattered electron image is 0.50% or more, and the following formula (1)
(A1/AV)≧1.50 (1)
is satisfied, the effect of suppressing the winding of thin paper around the fixing device during low-temperature fixing is exhibited. From the viewpoint of thin paper winding resistance during low-temperature fixing, a preferable condition is that the ratio of P1 to the total number of pixels of the backscattered 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, when the organosilicon polymer component is sufficiently present on the surface of the toner particles, the non-electrostatic adhesion to members such as the photosensitive drum and the intermediate transfer member can be kept low even during transfer in a high-temperature, high-humidity environment. be able to. When the non-electrostatic adhesion force is small, the responsiveness to the transfer voltage is increased, so that transfer dust is less likely to occur.
Here, the term "transfer faintness" refers to an image defect in which the in-plane uniformity of an image deteriorates due to the presence of toner that is not transferred here and there when an image of uniform density is output. Depending on the polymerization conditions, the organosilicon polymer can form fine irregularities of several nanometers to several tens to hundreds of nanometers while maintaining a certain coverage on the surface of the toner particles. In addition, although the detailed chemical structure will be described later, the organosilicon polymer preferably has a hydrophobic organic group such as a hydrocarbon group, which results in a low surface energy.

Although the mechanism is not clear, it is believed that the presence of the organosilicon polymer on the surface of the toner particles acts as an efficient spacer, reducing the frequency and adhesive force with which the toner particle base contacts members. Further, as a preferred embodiment, when a hydrophobic organic group such as a hydrocarbon group is present in the organosilicon polymer, charging stability in a high-temperature and high-humidity environment is improved. Moreover, the organosilicon polymer preferably has a siloxane bond, which allows it to exist on the surface of the toner particles as a surface layer having a strong covalent bond.
In the present invention, the ratio of P2 to the total number of pixels of the backscattered electron image is 0.50% or more, and the following formula (2)
(A2/AV)≧1.50 (2)
When satisfying , the effect of suppressing transfer blurring after endurance in a high-temperature and high-humidity environment is exhibited. Further, the ratio of P2 to the total number of pixels of the backscattered electron image is 0.70% or more and 5.00% or less, and the following formula (4)
4.00≧(A2/AV)≧1.70 (4)
It is preferable to satisfy the above because it is more effective in suppressing the transfer blurring after durability in a high-temperature and high-humidity environment.

Here, AV in formulas (1) to (4) will be described. As described above, when the brightness histogram of the backscattered electron image is bimodal, the ideal mode of the present invention is a state in which the two peaks derived from the toner particle base and the organosilicon polymer are independent. . In that case, there is almost no overlap between the two peaks, and the number of AVs containing the minimum value V becomes infinitely small. However, in practice, a brightness histogram is obtained in which two peaks are connected, and the AV has a fixed number of pixels. Each pixel contained in the AV is then a gray value containing both matrix and organosilicon polymer components flowing from A1 and A2.

Specifically, when the organosilicon polymer exists as a thin film of several nanometers on the surface of the matrix of the toner particles, or when the surface of the organosilicon polymer is filmed by a low-melting-point/low-molecular-weight component derived from the matrix of the toner particles. For example, if you are In such a case, compared with the case where the mother of the toner particles and the organosilicon polymer are localized with high purity, the respective effects of the mother and the organosilicon polymer are reduced.
The smaller the AV, the greater the A1 and A2 and the more efficient localization of the toner particle matrix and the organosilicon polymer, respectively. That is, it is possible to achieve a toner that does not easily cause thin paper to wind around a fixing device even during low-temperature fixing, and that does not easily cause transfer dust even after durability in 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 determined by the monomer species of the organosilicon polymer, the reaction temperature during formation of the organosilicon polymer, and the reaction Control is possible by time, reaction solvent and pH.

It is preferable that the organosilicon polymer on the surface of the toner particles forms a network structure in which particles each composed of pixels having a luminance range of 0 or more (Bl-30) or less are meshed on the surface of the toner particles. That is, the organosilicon polymer forms a network structure on the surface of the toner particles. Bl-29) When divided into pixel groups B of 255 or more, it is preferable to observe a network structure of the pixel groups B with the pixel groups A as meshes.
Domains formed by the pixel group A (particles composed of pixels with a brightness of 0 or more (Bl-30) or less (hereinafter also referred to as particles A1)) have a number average area 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 Feret diameter is 60 nm or more and 200 nm or less. More preferably, the number average value of 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 Feret diameter is 60 nm or more and 150 nm or less.

As mentioned above, A1 is attributed to the matrix of the toner particles. When the organosilicon polymer on the surface of the toner particles has a network structure, pixel portions (white) with brightness (Bl-29) or more and 255 or less form a network, as shown in FIG. 2(a). Then, the domain (particle A1) portion composed of the pixel portion (black) having a brightness of 0 or more (Bl-30) or less where no organosilicon polymer exists forms a “mesh” of the network structure, and an isolated particle is detected as
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 Feret diameter. can do. At the time of fixing, the melting of the binder resin and the exudation of the release agent occur from the particle A1 portion, which is the base portion of the toner particles.

That is, when the area and Feret diameter of the domain (particle A1) formed by the pixel group A have a certain size, the binder resin melts from the toner particle base and the release agent seeps out appropriately during fixing. happens to As a result, a toner having excellent low-temperature fixability can be obtained. The Feret diameter here is the distance of the longest straight line connecting any two points on the boundary line of the outer periphery of the selected range. When the particle area is 2.00×10 ³ nm ² or more, or the Feret diameter is 60 nm or more, the binder resin melts and the release agent oozes out sufficiently, which is particularly advantageous for low-temperature fixability from the viewpoint of blistering. 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 Feret diameter is 200 nm or less, the binding resin melts and the release agent oozes out appropriately. In particular, it is advantageous for low-temperature fixability from the viewpoint of hot offset.
The area and Feret diameter of the domains formed by the pixel group A can be controlled by the monomer species of the organosilicon polymer, reaction temperature, reaction time, reaction solvent and pH during formation of the organosilicon polymer.
It can be confirmed by the following method that the organosilicon polymer on the surface of the toner particles forms a network structure with the pixel group A as a network. From the backscattered electron image, when obtaining a binarized image in which the pixel portion in the luminance range of 0 or more (Bl-30) or less is black, if it 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 portions (white) above the luminance range (Bl-29) and below 255 are isolated like particles. detected. Particles A1 composed of pixel portions (black) in the luminance range of 0 or more (Bl-30) or less where no organosilicon polymer exists form a net. That is, when the organosilicon polymer on the surface of the toner particles does not form a net of network structure, the area and Feret diameter of the particles 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 (preferably an alkyl group) having 1 to 6 carbon atoms, or a vinyl-based polymer moiety containing a partial structure represented by formula (i) or formula (ii). (In formulas (i) and (ii), * represents a bonding site with the Si element in the RaT3 structure, and L in 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 bonding with Ra and the remaining three are involved in bonding with the O atom. The O atom constitutes a state in which both of its two valence electrons are involved in bonding with Si, that is, a siloxane bond (Si--O--Si). Considering Si atoms and O atoms as an organosilicon polymer, it is expressed as —SiO _3/2 because it has two Si atoms and three O atoms.
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 will be -SiO _1/2 (-OH) ₂ . Comparing these structures, more oxygen atoms forming a bridge structure with Si atoms is closer to the silica structure represented by SiO ₂ . Therefore, the more the —SiO _3/2 skeleton, the lower the surface free energy of the toner particle surface, which is excellent in environmental stability and member contamination resistance.

In addition, since Ra is a hydrophobic organic group, the presence of Ra keeps the surface free energy of the toner particle surface low, exhibiting excellent environmental stability.
The presence of the siloxane polymer moiety (--SiO _3/2 ) in the formula (RaT3) can be confirmed by ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble portion of the toner particles. The presence of Ra in the formula (RaT3) can be confirmed by ¹³ C-NMR measurement of the tetrahydrofuran-insoluble portion of the toner particles.
The structure can be controlled by the type and amount of the monomer species of the organosilicon polymer, reaction temperature, reaction time, reaction solvent and pH during formation of the organosilicon polymer.

Examples of the production of organosilicon polymers include the sol-gel method. 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 hydrolyzed and polycondensed in a solvent to form a sol. It is a method of gelling through states. It is used in the synthesis of glasses, ceramics, organic-inorganic hybrids, and nanocomposites. By using this production method, functional materials in various shapes such as surface layers, fibers, bulk bodies, and fine particles can be produced from the liquid phase at a low temperature. The organosilicon polymer is preferably produced by hydrolysis and polycondensation of a silicon compound represented by alkoxysilane (preferably a compound represented by the following formula (Z)).

Furthermore, the sol-gel method starts from a solution and forms a material by gelling the solution, so various microstructures and shapes can be produced. 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 the hydrophilicity of the hydrophilic group such as the silanol group 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 the silicon compound, and the like.
It is generally known that in a 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 electrophilically add to the oxygen of one reactive group (eg, an alkoxy group). Then, the oxygen atoms in the water molecules coordinate to the silicon atoms and become hydroxy groups through a substitution reaction. When enough water is present, one hydrogen ion attacks one oxygen of a reactive group (for example, an alkoxy group). Then, the substitution reaction to the hydroxy group slows down. Therefore, a polycondensation reaction occurs before all the reactive groups attached to the silane are hydrolyzed, and a one-dimensional linear polymer or a two-dimensional polymer tends to be produced relatively easily.

On the other hand, when the medium is alkaline, hydroxide ions add to silicon via a pentacoordinated intermediate. Therefore, all reactive groups (for example, alkoxy groups) are likely to leave and are easily substituted with silanol groups. In particular, when a silicon compound having three or more reactive groups in the same silane is used, hydrolysis and polycondensation occur three-dimensionally, forming an organosilicon polymer with many three-dimensional crosslinks. . Also, the reaction is completed in a short time.
Therefore, in order to form an organosilicon polymer, it is preferable to proceed with the sol-gel reaction in an alkaline reaction medium. preferable. This makes it possible to form a stronger and more durable organosilicon polymer.

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

(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 1 to 3 carbon atoms). below) represents an alkoxy group.)
Note that Ra is a functional group that becomes Ra in the RaT3 structure, and includes structures 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 formulas (iii) and (iv), * represents a bonding site with the Si element in the Z structure, and L in formula (iv) is an alkylene group (preferably a methylene group) or an arylene group (preferably phenylene group).)
Hydrophobicity can be improved by the organic group of Ra, and toner particles having excellent 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 form a crosslinked structure through hydrolysis, addition polymerization, and condensation polymerization, and a toner excellent in member contamination resistance and development durability can be obtained. It is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group, from the viewpoints of moderate hydrolyzability at room temperature and deposition and coating properties on the surface of the toner particles. Also, the 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.
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 above formula (Z) (hereinafter also referred to as trifunctional silane ) may be used singly or in combination.

Formula (Z) includes the following.
Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyldiethoxymethoxysilane, Vinylethoxydimethoxysilane, Vinyltrichlorosilane, Vinylmethoxydichlorosilane, Vinylethoxydichlorosilane, Vinyldimethoxychlorosilane, Vinylmethoxyethoxychlorosilane, Vinyldiethoxychlorosilane, Vinyl Triacetoxysilane, Vinyldiacetoxymethoxysilane, Vinyldiacetoxyethoxysilane, Vinylacetoxydimethoxysilane, Vinylacetoxymethoxyethoxysilane, Vinylacetoxydiethoxysilane, Vinyltrihydroxysilane, Vinylmethoxydihydroxysilane, Vinylethoxydihydroxysilane, Vinyldimethoxysilane trifunctional vinylsilanes such as hydroxysilane, vinylethoxymethoxyhydroxysilane, vinyldiethoxyhydroxysilane; allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, allylethoxydimethoxysilane, allyltrichlorosilane, allyl Methoxydichlorosilane, allylethoxydichlorosilane, allyldimethoxychlorosilane, allylmethoxyethoxychlorosilane, allyldiethoxychlorosilane, allyltriacetoxysilane, allyldiacetoxymethoxysilane, allyldiacetoxyethoxysilane, allylacetoxydimethoxysilane, allylacetoxymethoxyethoxysilane , allylacetoxydiethoxysilane, allyltrihydroxysilane, allylmethoxydihydroxysilane, allylethoxydihydroxysilane, allyldimethoxyhydroxysilane, allylethoxymethoxyhydroxysilane, allyldiethoxyhydroxysilane; p- styryltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyl Diethoxychlorosilane, Methyltriacetoxysilane, Methyldiacetoxymethoxysilane, Methyldiacetoxyethoxysilane, Methylacetoxydimethoxysilane, Methylacetoxymethoxyethoxysilane, Methylacetoxydiethoxysilane trifunctional methylsilanes such as trifunctional methylsilanes, such as silane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane; ethyltrimethoxysilane, ethyltrihydroxysilane; trifunctional ethylsilanes such as ethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane; propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, trifunctional propylsilanes such as; trifunctional butylsilanes such as butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane; hexyltrimethoxysilane, hexyltri trifunctional hexylsilanes such as ethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane; phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane; Trifunctional phenylsilanes such as. An organic silicon compound may be used independently and may use two or more types together.

As a result of hydrolysis and polycondensation, the content of the organosilicon compound having the structure represented by 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), an organic silicon compound 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:

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-(aminoethyl)-3 -aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane Silane, 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)trifluoroacetamide, trimethylsilyltrifluoromethanesulfonate, 1,3-dichloro-1 , 1,3,3-tetraisopropyldisiloxane, trimethylsilylacetylene, hexamethyldisilane, 3-isocyanatopropyltriethoxysilane, tetraisocyanatosilane, methyltriisocyanatosilane, vinyltriisocyanatosilane.

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

The coloring agent is not particularly limited, and the following known coloring agents can be used.
Yellow pigments include yellow iron oxide, navels yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, condensed azo compounds such as 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 orange pigments include the following. Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Benzidine Orange G, Indanthrene Brilliant Orange RK, Indanthrene Brilliant Orange GK.

Red pigments include condensation of red iron oxide, permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red C, lake red D, brilliant carmine 6B, brilliant carmine 3B, eosin lake, rhodamine lake B, and alizarin lake. 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 copper phthalocyanine compounds and their derivatives such as alkali blue lake, victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, and indanthrene blue BG, anthraquinone compounds, and basic dyes. A lake compound etc. are mentioned. Specific examples include the following. C. I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66.

Purple pigments include Fast Violet B and Methyl Violet Lake.
Examples of green pigments include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. White pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of black pigments include carbon black, aniline black, non-magnetic ferrite, magnetite, and those toned black using the above yellow, red, and blue colorants. These colorants can be used singly or in combination, or in the form of a solid solution.
The content of the colorant is preferably 3.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer forming the binder resin.

The release agent is not particularly limited, and known agents shown below can be used.
Paraffin wax, microcrystalline wax, petroleum wax and its derivatives such as petrolatum, montan wax and its derivatives, Fischer-Tropsch hydrocarbon wax and its derivatives, polyolefin waxes such as polyethylene and polypropylene and their derivatives, 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, vegetable waxes , animal wax, silicone resin. Derivatives include oxides, block copolymers with vinyl-based monomers, and graft-modified products. These can be used singly 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 forming the binder resin.

The toner particles may contain a charge control agent, and a known agent can be used. The amount of these charge control agents to be added 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 forming the binder resin.

If necessary, various organic or inorganic fine powders may be externally added to the toner particles. 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 from the viewpoint of durability when added to the toner particles.
As the organic or inorganic fine powder, for example, the following are used.
(1) Fluidity imparting agents: silica, alumina, titanium oxide, carbon black and carbon fluoride.
(2) Abrasives: metal oxides (e.g. strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitrides (e.g. silicon nitride), carbides (e.g. silicon carbide), metal salts (e.g. calcium sulfate, sulfuric acid) barium, calcium carbonate).
(3) Lubricant: fluororesin powder (eg, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (eg, zinc stearate, calcium stearate).
(4) Charge control particles: metal oxides (eg, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

The organic or inorganic fine powder may be surface-hydrophobized to improve the fluidity of the toner and uniformize the charge of the toner particles. Treatment agents for hydrophobic treatment of organic or inorganic fine powder include unmodified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, Organotitanium compounds may be mentioned. These treating agents may be used alone or in combination.

Specific methods for producing the toner will be described below, but the present invention is not limited to these.
The first manufacturing method is a method of obtaining toner particles by forming a surface layer of an organosilicon polymer in an aqueous medium after obtaining toner base particles. This method is preferable because the organosilicon compound is precipitated/polymerized in the vicinity of the surface of the toner base particles, so that a layer containing the organosilicon polymer can be efficiently formed on the toner particle surfaces.
Specifically, 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 at a concentration such that the solid content of the base particles is 10% by mass or more and 40% by mass or less with respect to the total amount of the base particle dispersion liquid. Further, it is preferable to adjust the temperature of the base particle dispersion to 35° C. or higher. Furthermore, the pH of the base particle dispersion is adjusted to a pH at which condensation of the organosilicon compound does not easily proceed. 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 around the pH at which the reaction is most difficult to proceed.
Next, it is preferable to use the organosilicon compound that has been hydrolyzed. For example, an organosilicon compound is hydrolyzed in a separate container. When the amount of the organosilicon compound is 100 parts by mass, the concentration of hydrolysis is preferably 40 parts by mass or more and 500 parts by mass or less of water from which ions are removed, such as ion-exchanged water or RO water, more preferably 100 parts by mass of water. It is more than 400 mass parts or less. The hydrolysis conditions are preferably pH 1.0 to 7.0, temperature 15 to 80° C., and time 1 to 600 minutes.
Then, the hydrolyzed organosilicon compound is added to the base particle dispersion. The base particle dispersion and the organosilicon compound hydrolyzate are stirred and mixed, and the mixture is preferably maintained at 35° C. or higher for 3 minutes or more and 120 minutes or less. Thereafter, the pH is adjusted to be suitable for condensation (preferably pH 6.0 or higher or 3.0 or lower, more preferably pH 8.0 or higher), and the organosilicon compound is condensed at once, preferably at 35° C. or higher for 60 minutes or longer. It is preferable 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 is given below.
(1) Suspension polymerization method: A polymerizable monomer composition containing a polymerizable monomer capable of forming a binder resin, a release agent, and, if necessary, a colorant, etc. is granulated in an aqueous medium. Then, the polymerizable monomer is polymerized to obtain toner base particles.
(2) Pulverization method: toner base particles are obtained by melting and kneading a binder resin, a release agent, and optionally a colorant and the like and pulverizing the mixture.
(3) Dissolution suspension method: An organic phase dispersion prepared by dissolving a binder resin, a release agent, and optionally a colorant in an organic solvent is suspended in an aqueous medium, granulated, By removing the organic solvent after the polymerization, toner base particles are obtained.
(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, etc. is mixed in an aqueous medium. In this method, toner particles are obtained by granulating and polymerizing the polymerizable monomer.
As the third manufacturing method, a binder resin, an organic silicon compound, a releasing agent, and, if necessary, a coloring agent, etc. are dissolved/dispersed in an organic solvent to prepare an organic phase dispersion, which is then suspended in an aqueous medium. , granulation and polymerization, followed by removal of the organic solvent to obtain toner particles.

The fourth manufacturing method is a method in which binder resin particles, sol- or gel-state organosilicon compound-containing particles, and, if necessary, colorant particles are aggregated and associated in an aqueous medium to form toner particles. .
As the fifth manufacturing method, a solvent having an organic silicon compound 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 form a surface layer containing the organic silicon compound. is a method of forming
In addition, the following are mentioned as an aqueous medium. water; a mixed solvent of water and an alcohol such as methanol, ethanol, or propanol; and the like.

As the method for producing toner particles, among the above-described production methods, the first production method, in which toner base particles are produced by a suspension polymerization method, is most preferable. In the suspension polymerization method, the organosilicon polymer is easily deposited uniformly on the surface of the toner particles, and the environmental stability, development transferability, and their durability are improved. The suspension polymerization method will be further described below.
If necessary, other resins may be added to the polymerizable monomer composition. 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 second half of the polymerization step. Furthermore, in order to remove unreacted polymerizable monomers or by-products, it is also possible to partially distill off the dispersion medium from the reaction system in the second half of the polymerization process or after the completion of the polymerization process. The surface layer containing the organosilicon polymer may be formed by using a base particle dispersion in which the toner base particles are dispersed without washing, filtering and drying after the polymerization step.

As the above other resins, the following resins can be used as long as they do not affect the effects of the present invention.
Homopolymers of styrene and substituted products thereof such as polystyrene and polyvinyltoluene; styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, 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-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Styrenic copolymers such as coalescence, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, poly Vinyl 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 singly or in combination.

As the polymerizable monomer in the above suspension polymerization method, the following vinyl-based polymerizable monomers can be suitably exemplified. 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-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; methyl acrylate; , ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n - acrylic polymerizable monomers such as 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, vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.
Among these monomers, styrene, styrene derivatives, acrylic polymerizable monomers and methacrylic polymerizable monomers are preferred.

Moreover, a polymerization initiator may be added in the polymerization of the polymerizable monomer. Examples of polymerization initiators include the following. 2,2'-azobis-(2,4-divaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis -Azo or diazo polymerization initiators such as 4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxide 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 weight per 100 parts by weight of the polymerizable monomer, and may be used alone or in combination.
In order to control the molecular weight of the binder resin that constitutes 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 cross-linking agent may be added during the polymerization of the polymerizable monomer. Examples of crosslinkable monomers include the following. 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 diacrylates, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and methacrylates of the above acrylates.
Examples of polyfunctional crosslinkable monomers include the following. pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis(4-methacryloxy-polyethoxyphenyl)propane, diacryl phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diarylchlorendate. 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 a 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 .
Moreover, the following are mentioned as an organic dispersing agent. polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose,
Sodium salt of carboxymethylcellulose, 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.

Various measurement methods related to the present invention are described below.
When organic fine powder or inorganic fine powder is externally added to the toner, a toner obtained by removing the organic fine powder or 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 in a hot water bath to prepare a concentrated sucrose solution. In a centrifugation tube (capacity 50 ml), 31 g of the concentrated sucrose solution and Contaminon N (a neutral detergent for washing precision measuring instruments with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) were added. 6 mL of a 10% by mass aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added. 1.0 g of toner is added thereto, and the lumps of toner are loosened with a spatula or the like. The tube for centrifugation is shaken for 20 minutes at 300 spm (strokes per min) in a shaker (AS-1N, sold by As One Co., Ltd.). After shaking, the solution is replaced in a swing rotor glass tube (50 mL) and separated in a centrifuge (H-9R manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes.
This operation separates the toner particles and the external additive. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the separated toner on the uppermost layer is collected with a spatula or the like. After the collected toner is filtered with a vacuum filter, it is dried with a dryer for 1 hour or more to obtain a sample for measurement. This operation is carried out multiple times to ensure the required amount.

<Method for Acquiring Backscattered Electron Image of Surface of Toner Particle>
A backscattered electron image of the surface of the toner particles was obtained with a scanning electron microscope (SEM).
The SEM apparatus and observation conditions are as follows.
Apparatus used: ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd.
Accelerating voltage: 1.0 kV
WD: 2.0mm
Aperture Size: 30.0 μm
Detection signal: EsB (energy selective backscattered electron)
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: Sprinkle toner particles on carbon tape (no vapor deposition)
Determine contrast and brightness according to the following procedure. First, the contrast is set so that the two maximum values P1 and P2 have as many pixels as possible 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 skirts of the two peaks having P1 and P2 as the maximum values fall within the luminance histogram. These contrast and brightness are appropriately set according to the above-described procedure according to the state of the device used. Further, 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 backscattered electrons. . The observation field is selected near the vertex 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 elemental mapping image by energy dispersive X-ray spectroscopy (EDS) obtained with a scanning electron microscope (SEM) and the backscattered electron image.
The SEM/EDS apparatus and observation conditions are as follows.
Apparatus used (SEM): ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd.
Apparatus used (EDS): NORAN System 7, Ultra Dry EDS Detector manufactured by Thermo Fisher Scientific Co., Ltd.
Accelerating 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
Pretreatment: Toner particles are scattered on a carbon tape and platinum sputtered. The mapping image of the silicon element obtained by this method is superimposed on the backscattered electron image, and the silicon atom part of the mapping image matches the bright part of the backscattered electron image. make sure that

<Method of obtaining luminance histogram>
The luminance histogram is obtained by analyzing the backscattered electron image of the surface of the toner particles obtained by the above method using image processing software ImageJ (developed by Wayne Rashand). The procedure is shown below.
First, the backscattered electron image to be analyzed is converted to 8-bit from Type in the Image menu. Next, from Filters in the Process menu, set the median diameter to 2.0 pixels to reduce image noise. Estimate the center of the image after excluding the observation condition display part displayed at the bottom of the backscattered electron image, and select a 1.5 μm square range from the image center of the backscattered electron image using the Rectangle Tool on the toolbar. .
Next, select Histogram from the Analyze menu to display the brightness histogram in a new window. The numerical value of the brightness histogram is obtained from the list of the window. If necessary, fitting of the luminance histogram may be performed. From this, the luminance and the number of pixels giving the maximum values P1 and P2, the luminance Bl giving the minimum value V, and the numbers of pixels A1, A2 and AV are calculated.
The above procedure was performed for 10 fields of view for the toner particles to be evaluated, and the average value of each was taken as the physical property value of the toner particles obtained from the brightness histogram.

<Method of analyzing domain formed by pixel group A (calculating area and Feret diameter)>
Analysis of the domain (particle A1) formed by the pixel group A is performed by using image processing software ImageJ (developed by Wayne Rashand) for the backscattered electron image of the surface of the toner particle obtained by the above method. The procedure is shown below.
First, convert the backscattered electron image to 8-bit from Type in the Image menu. Next, from Filters in the Process menu, set the median diameter to 2.0 pixels to reduce image noise. Estimate the center of the image after excluding the observation condition display part displayed at the bottom of the backscattered electron image, and select a 1.5 μm square range from the image center of the backscattered electron image using the Rectangle Tool on the toolbar. .
Next, select Threshold from Adjust in the Image menu. In manual operation, select all pixels falling within the luminance range of 0 or more (Bl-30) or less, and click Apply to obtain a binarized image. This operation causes the pixels corresponding to A1 to be displayed in black. Again, the center of the image is estimated after excluding the observation condition display part displayed at the bottom of the backscattered electron image, and the range of 1.5 μm square from the image center of the backscattered electron image is estimated using the Rectangle Tool on the toolbar. select.
Next, using the straight line tool (Straight Line) on the tool bar, select the scale bar in the observation condition display section displayed below the backscattered electron image. If Set Scale is selected from the Analyze menu in that state, a new window opens and the pixel distance of the selected straight line is entered 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. Particle analysis is performed by selecting Analyze Particles from the Analyze menu, checking Display Result, and clicking OK. From the newly opened Results window, the particle area (Area) and the particle Feret diameter (Feret) for each particle corresponding to the domain (particle A1) formed by the pixel group A are obtained, and the number average value is calculated.
The above procedure is performed for 10 fields of view for each toner particle to be evaluated, and the arithmetic mean value of each field is used.

<Method for Confirming Network Structure of Organosilicon Polymer>
The organosilicon polymer on the surface of the toner particles has a network structure of particles composed of pixels having a luminance range of 0 or more (Bl-30) or less on the toner particle surface (a pixel group A is a mesh, 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 is obtained in which the pixel portion in the luminance range of 0 or more (Bl-30) or less is black. . 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 Diameter (D4) of Toner Particles>
The weight-average particle diameter (D4) of the toner particles was measured using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting conditions and analyzing measurement data, the number of effective measurement channels is 25,000. was calculated by analyzing
As the electrolytic aqueous solution used for measurement, a solution obtained by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used.
Before performing measurement and analysis, the dedicated software is set as follows. In the "change standard measurement method (SOM) screen" of the dedicated software, set the total number of counts in control mode to 50000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter Co., Ltd. (manufactured) to set the value obtained using By pressing the threshold/noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of aperture tube after measurement. In the "pulse-to-particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

A specific measuring method is as follows.
(1) About 200 mL of the electrolytic aqueous solution is placed in a 250 mL glass round-bottomed beaker exclusively for Multisizer 3, set on a sample stand, and stirred counterclockwise at 24 rpm with a stirrer rod. Then, remove the dirt and air bubbles inside the aperture tube using the dedicated software's "Flush Aperture Tube" function.
(2) About 30 mL of the electrolytic aqueous solution is placed in a 100 mL flat-bottom glass beaker, and "Contaminon N" (a nonionic surfactant, an anionic surfactant, and an organic builder consisting of an organic builder) is used as a dispersant. About 0.3 mL of a diluent obtained by diluting a 10% by mass aqueous solution of a neutral detergent for washing ware (manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water three times by mass is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with a phase shift of 180 degrees, and an ultrasonic disperser with an electrical output of 120 W "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) in a water tank. A predetermined amount of ion-exchanged water is put into the water tank, and about 2 mL of the contaminon 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. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) About 10 mg of toner particles are added little by little to the aqueous electrolytic solution in the beaker of (4) while the aqueous electrolytic solution is being irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank is appropriately adjusted to 10°C or higher and 40°C or lower.
(6) The electrolytic aqueous solution of (5) above, in which toner particles are dispersed, is dropped into the round-bottomed beaker of (1) above set in the sample stand, and adjusted so that the measured concentration is about 5%. do. The measurement is continued until the number of measured particles reaches 50,000.
(7) Analyze the measurement data with the dedicated software attached to the apparatus, and calculate the weight average particle size (D4). The weight average particle diameter (D4) is the "average diameter" on the analysis/volume statistics (arithmetic mean) screen when graph/vol% is set using dedicated software.

<Method for Confirming Structure Represented by Formula (RaT3)>
The structure of the organosilicon polymer represented by the formula (RaT3) is confirmed using a nuclear magnetic resonance spectrometer (NMR).
A sample for NMR measurement is prepared as follows.
Preparation of measurement sample: 10.0 g of toner particles were weighed, placed in a filter paper thimble (No. 86R manufactured by Toyo Roshi Kaisha Ltd.), put in a Soxhlet extractor, and extracted with 200 ml of tetrahydrofuran as a solvent for 20 hours. was vacuum-dried at 40° C. for several hours to obtain a sample for NMR measurement.

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

In the structure represented by the formula (RaT3), the siloxane bond portion was confirmed by ²⁹ Si-NMR (solid) measurement. Measurement conditions are shown below.
" ²⁹ Si-NMR (solid) measurement conditions"
Device: JNM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran-insoluble matter of toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measured 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
Cumulative number of times: 2000 to 8000 times After the above measurement, a plurality of silane components having different substituents and bonding groups in the tetrahydrofuran-insoluble portion of the toner particles were curve-fitted into the following X1 structure, X2 structure, X3 structure, and X4 structure. Separate the peaks and calculate the respective 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

(Ri, Rj, Rk, Rg, Rh, and Rm in formulas (5) to (8) are organic groups such as hydrocarbon groups having 1 to 6 carbon atoms bonded to a silicon atom, halogen atoms, hydroxy group, acetoxy group or alkoxy group).
In formulas (5) to (8), the structures enclosed by rectangles are X1 structure to 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 preferably 40% or more and 80% or less.
When the structure represented by the formula (RaT3) needs to be confirmed in more detail, it may be identified by the ¹ H-NMR measurement results together with the ¹³ C-NMR and ²⁹ Si-NMR measurement results.

The present invention will be described in more detail below with specific production examples, working examples, and comparative examples, but these are not intended to limit the present invention in any way. In addition, "parts" in the following prescriptions are based on mass unless otherwise specified.

[Manufacturing Example of Toner 1]
<Step of preparing aqueous medium 1>
To 1000.0 parts of ion-exchanged water in a reaction vessel, 14.0 parts of sodium phosphate (12 hydrate, manufactured by Rasa Kogyo Co., Ltd.) was added, and the mixture was kept at 65° C. for 1.0 hour while purging with nitrogen. T. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, a calcium chloride aqueous solution obtained by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water is mixed together. to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 10% by mass hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0, and an aqueous medium 1 was obtained.

<Preparation step 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 Kakoki Co., Ltd.), and zirconia particles with a diameter of 1.7 mm were dispersed at 220 rpm for 5.0 hours to obtain a pigment. 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 (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 (3,5-di-tert-butylsalicylic acid aluminum compound)
This was kept at 65° C. and T.I. K. A homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to uniformly dissolve and disperse at 500 rpm to prepare a polymerizable monomer composition.

<Step of preparing organic silicon compound aqueous solution>
60.0 parts of ion-exchanged water was weighed into a reactor equipped with a stirrer and a thermometer, 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. After that, 40.0 parts of methyltriethoxysilane was added and stirred for 2 minutes to obtain an aqueous organosilicon compound solution 1.

<Granulation process>
While maintaining the temperature of the aqueous medium 1 at 70° C. and the rotation speed of the stirring device at 12000 rpm, the polymerizable monomer composition is added to the aqueous medium 1, and t-butyl peroxypivalate as a polymerization initiator9. 0 parts were added. The mixture was granulated for 10 minutes while maintaining 12000 rpm with the stirring device.

<Polymerization process>
The agitator was changed from the high-speed agitator to a propeller agitating blade, and the polymerization reaction was carried out by maintaining the temperature at 70°C while stirring at 150 rpm for 5.0 hours, and heating the mixture to 95°C for 2.0 hours. to obtain a slurry of toner particles. After that, the temperature of the slurry was cooled to 60° C. and the pH was measured to be pH=5.0. 20.0 parts of organosilicon compound aqueous solution 1 was added while stirring was continued at 60°C. After holding for 30 minutes as it is, the slurry was adjusted to pH=9.0 using an aqueous sodium hydroxide solution and held for an additional 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 slurry of toner particles is cooled, and hydrochloric acid is added to the slurry of toner particles to adjust the pH to 1.5 or less, and the mixture is left with stirring for 1 hour, followed by solid-liquid separation with a pressurized filter to form a toner cake. got This was reslurried with ion-exchanged water to form a dispersion again, and then subjected to solid-liquid separation with the aforementioned filter. After reslurry and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS/cm or less, solid-liquid separation was finally performed to obtain a toner cake.
The obtained toner cake was dried with a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.).
The drying conditions were a blowing temperature of 90.degree. C., a dryer outlet temperature of 40.degree. In this example, the obtained toner particles 1 were used as the toner 1 as they were without being externally added. It was confirmed by the method described above that Toner 1 has a surface layer containing an organosilicon polymer on the surface of the toner particles. Table 2 shows the physical properties of the obtained toner.

[Manufacturing Examples of Toners 2 to 19 and Comparative Toners 1, 2, 5, and 6]
Toners 2 to 19 and Comparative Toners 1, 2, 5, and 6 were obtained in accordance with the recipes and production conditions shown in Table 1 and in the same manner as in the production example of Toner 1 above. Table 2 shows the physical properties of the obtained toner.

[Production Example of Comparative Toner 3]
In the production example of Toner 1, 12.0 parts of methyltriethoxysilane was added as a monomer to the pigment dispersion in the step of preparing the polymerizable monomer composition. The preparation step of the organosilicon compound aqueous solution was not performed. No hydrolysis solution was added in the polymerization step, and only pH adjustment and subsequent maintenance were performed. Comparative Toner 3 was prepared in the same manner as in Toner 1 except for the above. 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 Comparative Toner 3, except that the amount of methyltriethoxysilane was changed to 7.4 parts. Table 2 shows the physical properties of the obtained toner.

[Production Example of Comparative Toner 7]
In the manufacturing example of Toner 1, the step of preparing the organosilicon compound aqueous solution was not performed. After obtaining a slurry of toner particles in the polymerization step, the temperature of the slurry was cooled to 60° C., and 8.0 parts of methyltriethoxysilane was added as a monomer while stirring was continued. After holding for 30 minutes as it is, the slurry was adjusted to pH=9.0 using an aqueous sodium hydroxide solution and held for an additional 300 minutes to form an organosilicon polymer on the surface of the toner particles. Comparative Toner 7 was prepared in the same manner as in Toner 1 except for the above. 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 Production Example, except that the amount 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 manufacturing example of Toner 1, the step of preparing the organosilicon compound aqueous solution was not performed. After obtaining a slurry of toner particles in the polymerization step, the temperature of the slurry was cooled to 25° C. and 250 parts of methyltriethoxysilane was added as a monomer while stirring was continued. Furthermore, 4000.0 parts of deionized water was added. After holding this solution for 30 minutes, p
The mixture 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 surface of the toner particles. Comparative Toner 9 was prepared in the same manner as in Toner 1 except for the above. 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 laser beam printer LBP9600C manufactured by Canon 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. under normal temperature and normal humidity (25° C./50% RH) environment at a process speed of 300 mm/sec. For the toner to be evaluated, a solid image was formed on an image-receiving paper with a toner load of 0.40 mg/cm ² , and heated and pressed without oil to form a fixed image on the image-receiving paper. At this time, the state of the paper passing was visually confirmed, and the temperature of the fixing device when the paper was passed without winding was examined, and the winding property during low-temperature fixing was evaluated based on the following criteria. GF-600 (weight: 60 g/m ² , sold by Canon Marketing Japan Inc.) was used as the receiving paper.
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 higher was judged to be good.

<Evaluation of transfer distortion>
A tandem type laser beam printer LBP9600C manufactured by Canon having the configuration shown in FIG. A toner cartridge for LBP9600C was filled with 200 g of the toner to be evaluated, and the toner cartridge was left for 24 hours in a high-temperature and high-humidity (32.5° C./85% RH) environment.
After being left for 24 hours, the toner cartridge was attached to the LBP9600C, and images with a printing ratio of 1.0% were printed out up to 15,000 sheets of A4 paper in the horizontal direction. After outputting 15,000 sheets, a solid image with a toner load of 0.40 mg/cm ² was output to CS-680 (basis weight of 68 g/m ² , sold by Canon Marketing Japan Inc.). This image was visually observed, and the transfer blur was evaluated based on the following criteria. Incidentally, in the present invention, the portion where the image uniformity is impaired was judged as transfer blur.
In addition, the code|symbol in FIG. 3 is as follows.
1: photoreceptor, 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 Apparatus 11: Stirring blade 12: Drive roller 13: Transfer roller 14: Bias power supply 15: Tension roller 16: Transfer/transport belt 17: Driven roller 18: Paper 19: Paper feed roller 20: Adsorption roller 21: Fixing device A: Transfer smears are not seen under normal light or when held up to strong light. B: Transfer smudges are not seen under normal light, but when held up to strong light. C: 1 to 2 transfer smudges are observed even under normal light, but no white spots are observed. D: 3 to 4 transfer smudges are observed even under normal light, but white spots are observed. No omission observed E: Even under normal light, 5 or more transfer smudges or 1 or more white spots were observed.

<Evaluation of Low Temperature Fixability>
In the same manner as the evaluation of the winding property at low temperature fixation, LBP9600C modified so that the fixation temperature can be adjusted was used at a process speed of 300 mm/sec at normal temperature and normal 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 was formed on an image-receiving paper with a toner load of 0.40 mg/cm ² , and heated and pressed without oil to form a fixed image on the image-receiving paper. Using a Kimwipe (S-200, manufactured by Crecia Co., Ltd.), the fixed image is rubbed 10 times with a load of 75 g/cm ² , and the temperature at which the image density decrease rate before and after rubbing is less than 5% is defined as the fixing temperature. was evaluated based on the criteria of
Business 4200 (weight: 105 g/m ² , manufactured by Xerox) was used as the image receiving paper. For the measurement of image density, a color reflection densitometer X-RITE404A (manufactured by X-Rite Co.) was used to measure the relative density of the white background portion of the printed image with a document density of 0.00, and the image density after rubbing. 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 higher was judged to be good.

[Examples 1 to 19, Comparative Examples 1 to 8]
Each toner shown in Tables 1 and 2 was evaluated for winding property during fixing at low temperature, transfer blurring, and low temperature fixing property. Table 3 shows the results.

1: photoreceptor, 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 Apparatus 11: Stirring blade 12: Drive roller 13: Transfer roller 14: Bias power supply 15: Tension roller 16: Transfer/transport belt 17: Driven roller 18: Paper 19: Paper feed roller 20: Adsorption roller, 21: fixing device

Claims (2)

A toner having toner particles having a binder resin and a release agent,
The toner particles have a surface layer containing an organosilicon polymer,
The organosilicon polymer is a polymer having a structure represented by the following formula (RaT3),

[In the formula (RaT3), Ra represents a hydrocarbon group having 1 to 6 carbon atoms. ]
In observing the surface of the toner particles with a scanning electron microscope, a backscattered electron image of a 1.5 μm square area of the surface of the toner particles is obtained, and the luminance of each pixel constituting the backscattered electron image is changed from 0 to 2.
When a luminance histogram is obtained by dividing into 55 256 gradations and having the horizontal axis as luminance and the vertical axis as the number of pixels, in the luminance histogram,
(i) there are two maximum values P1 and P2 and a minimum value V between the P1 and the P2, and the peak containing the P2 is a peak derived from the organosilicon polymer;
(ii) the luminance that gives the P1 is 20 or more and 70 or less;
(iii) the luminance that gives the P2 is 130 or more and 230 or less;
(iv) the ratio of the P1 and the P2 to the total number of pixels of the backscattered electron image is 0.50% or more;
(v) let Bl be the luminance that gives the V, let A1 be the total number of pixels in the luminance range of 0 or more (Bl-30) or less, and let AV be the total number of pixels in the luminance range of (Bl-29) or more (Bl+29) or less; When the total number of pixels in the luminance range (Bl + 30) or more and 255 or less is A2, the following formulas (1) and (2)
(A1/AV)≧1.50 (1)
(A2/AV)≧1.50 (2)
satisfy the
A toner characterized by: The organosilicon polymer forms a network structure on the surface of the toner particles,
In the backscattered electron image, when all the pixels are divided into a pixel group A with a luminance range of 0 or more (Bl-30) or less and a pixel group B with a luminance range of (Bl-29) or more and 255 or less, the pixel group A A network structure of the pixel group B is observed, with
A 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 particle Feret diameters is 60 nm or more and 200 nm or less;
The toner of claim 1.

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