JP2020071363A - toner - Google Patents

Abstract

To provide a toner which offers good solid followability, reduced transfer dust, and superior halftone reproducibility even in low temperature-low humidity environments.SOLUTION: A toner is provided, comprising toner particles containing a colorant and a binder resin, where a force between two particles is 1.0 to 25.0 nN, inclusive, when a compact of the toner formed by compressing the toner with a load of 78.5 N is measured, and a surface potential distribution of the toner as measured by a scanning probe microscope has a variation coefficient of 50% or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a toner used in an image forming method such as electrophotography.

The electrophotographic technique is a technique in which an electrostatic latent image is formed on a uniformly charged photoreceptor, and image information is visualized with charged toner, and is used in devices such as copying machines and printers. In recent years, copying machines and printers have been used in new market areas, and high image stability is required for use in various environments. In order to stabilize images, it is desirable for toner to be electrostatically and mechanically stabilized in copiers and printers, and toner should have a uniform charge distribution against electrostatic conveyance. High fluidity is demanded for high efficiency and mechanical transportation.
Patent Document 1 describes a toner in which the shapes of two types of magnetic powder to be added are specified in order to make the charge distribution between toner particles uniform. By reducing the amount of toner that has an excessive amount of charge and the amount of toner that has an opposite charge under a high temperature and high humidity environment, it is possible to suppress variations in the charge distribution between particles.
Patent Document 2 describes a toner in which the molecular weight of the binder resin is controlled in order to make the charge distribution in the toner particles have the same polarity. By making the surface potential the same polarity at all points on the toner surface, toner scattering and fogging can be suppressed.
Patent Document 3 describes a toner in which the interparticle force between the toner particles is controlled in order to improve the toner fluidity under a high temperature and high humidity environment.

JP, 2017-116792, A JP, 2016-126196, A JP, 2016-103005, A

However, in Patent Document 1, in a low-temperature and low-humidity environment, the water content of the toner is lowered and the electrical conductivity is lowered, so that the localized charge of the toner particles is difficult to diffuse throughout the toner. As a result, variations in the surface potential distribution within the toner particles increase, and there are problems that transfer dust (a phenomenon in which toner is scattered around a character or line image) occurs and halftone reproducibility deteriorates.
In the above-mentioned Patent Document 2, in a low-temperature and low-humidity environment, similarly to the toner in Patent Document 1, the localized charge of the toner particles is difficult to diffuse throughout the toner particles, and the dispersion of the surface potential distribution within the toner particles increases. However, there are problems such as occurrence of transfer dust and deterioration of halftone reproducibility. Further, since the chargeability of the toner surface is controlled by using a resin, there is a problem that when a high pressure is applied to the toner in a low temperature and low humidity environment, the fluidity is lowered and the solid followability is deteriorated.
In the above-mentioned Patent Document 3, fogging is suppressed in a high temperature and high humidity environment, but in a low temperature and low humidity environment, the electrostatic charge attracts the toner, whereby the toner agglomerates and the solid followability deteriorates. There was a problem called.
For the above reasons, there is a demand for a toner that has good solid followability even under a low temperature and low humidity environment, has less transfer dust, and has excellent halftone reproducibility.
Therefore, an object of the present invention is to provide a toner having excellent solid followability even under a low temperature and low humidity environment, less generation of transfer dust, and excellent halftone reproducibility.

The present invention provides a toner having toner particles containing a colorant and a binder resin,
The force between two particles is 1.0 nN or more and 25.0 nN or less when measuring a compact of the toner formed by compressing the toner with a load of 78.5 N.
In the surface potential distribution of the toner particles measured by a scanning probe microscope, the variation coefficient of the surface potential distribution is 50% or less.

  According to the present invention, it is possible to provide a toner having good solid followability even under a low temperature and low humidity environment, less transfer dust generation, and excellent halftone reproducibility.

(A) And (B) is a figure which shows an example of the apparatus used for measurement of the force between two particles.

  The toner of the present invention has a two-particle force of 1.0 nN or more and 25.0 nN or less when a compact of the toner formed by compressing the toner with a load of 78.5 N is measured, and is measured by a scanning probe microscope. In the surface potential distribution of the toner particles, the coefficient of variation of the surface potential distribution is 50% or less.

  Hereinafter, the present invention will be described in detail.

  In a low-temperature and low-humidity environment, toner is likely to be charged up in a printer or a copying machine, and a strong electrostatic repulsive force is generated between toner particles. As a result, the toner image may be biased and the halftone reproducibility may be deteriorated. Conventionally, as a method of suppressing charge-up of toner, a method of adding a material that leaks electric charge to the toner has been known.

  Excessive charge-up of the toner could be suppressed by adding a material that leaks charges. However, the halftone reproducibility was not significantly improved. Although the mechanism is not clear, the reason why the halftone reproducibility was not significantly improved is that the charge inside the toner particles partially leaks, causing variations in the electrostatic repulsion between the toner particles, resulting in uneven toner images. It is thought that this is due to

  Therefore, the inventors of the present invention considered that the problem of deterioration of halftone reproducibility in a low temperature and low humidity environment could be solved if uniform electrostatic repulsion acts between the toner particles on the developed photoreceptor. ..

  As a result of intensive studies by the present inventors, the toner has high fluidity under high pressure, and if the variation (variation coefficient) of the surface potential distribution within the toner particles is reduced, the halftone reproducibility is deteriorated in a low temperature and low humidity environment. It turns out that the problem can be solved.

  As a result of further studies, it was found that the problem of deterioration of halftone reproducibility can be solved by reducing the interparticle force of the toner in order to improve the fluidity of the toner under high pressure.

  It should be noted that in order to evaluate whether or not the halftone reproducibility is excellent, it is necessary to observe the halftone image, and in the examples described below, a solid white image obtained by dividing solid white to solid black into 256 gradations. From the 49th gradation image.

  In the toner of the present invention, the interparticle force in the toner compact formed by compressing the toner with a load of 78.5 N is 1.0 nN or more and 25.0 nN or less. The details of the measuring method will be described later, but after applying a weight of 78.5 N to the toner contained in the cell divided into upper and lower halves, the maximum tensile rupture force when the cell is ruptured causes The force is measured. The compression condition of 78.5 N is a value that assumes the load applied when the compacted toner in the cartridge passes through the regulation blade on the developing roller.

  Further, in the toner of the present invention, the coefficient of variation of the surface potential distribution of the toner particles measured by a scanning probe microscope is 50% or less. Although the details of the calculation method will be described later, the coefficient of variation of the surface potential distribution of the toner particles is calculated from the surface potential distribution measured by a KPFM (Kelvin probe force microscope) which is a kind of scanning probe microscope. First, the surface potential distribution of the toner particles is measured by applying a voltage to the probe so as to cancel the electrostatic force received by the probe brought close to the toner surface. The coefficient of variation of the surface potential distribution is calculated by dividing the standard deviation of the surface potential distribution by the average value.

  When the force between the two particles satisfies the above range, and the coefficient of variation of the surface potential distribution does not satisfy the above range, the toner particles under the low temperature and low humidity environment do not aggregate even if they are subjected to a high pressure by the regulating blade on the developing roller, The toner particles are developed in an isolated state. However, due to variations in electrostatic repulsion between the toner particles, the toner is unevenly distributed on the photoconductor, and halftone reproducibility is not improved. When the coefficient of variation of the surface potential distribution satisfies the above range and the interparticle force does not satisfy the above range, the toner particles on the photoconductor are not isolated in a low temperature and low humidity environment, and toner particle aggregates are present. Therefore, the toner particles around the aggregate receive a strong electrostatic force. As a result, the deviation of the toner was increased, and the halftone reproducibility was not improved.

  On the other hand, when both the two-particle force and the coefficient of variation of the surface potential distribution satisfy the above ranges, the toner particles are developed in an isolated state, and the developed toner particles have a uniform static charge according to the surface potential distribution. Repulsive force occurs. As a result, the deviation of the toner on the photosensitive member is significantly reduced for the first time, and the halftone reproducibility is improved.

  Further, when the force between the two particles is in the above range, the toner on the developing roller does not aggregate even in a low temperature and low humidity environment, and the solid followability becomes good. More preferably, the force between the two particles is 1.0 nN or more and 20.0 nN or less.

  Further, by setting the coefficient of variation of the surface potential distribution within the above range, the ratio of the image force acting on the toner and the photoconductor and the electrostatic attractive force generated by the transfer bias is stable for each toner even in a low temperature and low humidity environment. By keeping it constant, the transfer dust becomes good. More preferably, the coefficient of variation of the surface potential distribution is 33% or less.

  The toner particles of the present invention preferably have an absolute value of the average value of the surface potential distribution of 1.0 V or more and 15.0 V or less. When the absolute value of the average value of the surface potential distribution is within the above range, a stable electrostatic repulsive force is exerted on the toner particles even under a high temperature and high humidity environment, and the halftone reproducibility is improved. More preferably, the absolute value of the average value of the surface potential distribution is 2.0 V or more and 10.0 V.

  One means for adjusting the coefficient of variation between the two-particle force and the surface potential distribution within the scope of the present invention is to have, for example, a surface layer containing an organosilicon polymer. By including the organosilicon polymer in the surface layer, the contact area between the toners is reduced and the interparticle force can be reduced. Furthermore, the organosilicon polymer has a suitable electric conductivity. As a result, by containing the organosilicon polymer in the surface layer, the localized charges generated in the toner by frictional charging are diffused throughout the toner, and the coefficient of variation of the surface potential distribution can be reduced. As a material selection, the coefficient of variation between the two-particle force and the surface potential distribution can be adjusted by the number of carbon atoms directly bonded to the silicon atom of the organosilicon polymer and the carbon chain length. In addition, it is possible to control the coefficient of variation between the two-particle force and the surface potential distribution by adjusting the uneven shape of the surface layer containing the organosilicon polymer or the network structure connecting the projections. These adjustments can be made depending on the timing and form of adding the organosilicon polymer, the pH, temperature, time, etc. when pretreating the organosilicon polymer.

  The following method is particularly preferred in the present invention. First, toner base particles are prepared and dispersed in an aqueous medium. Furthermore, the pH of the dispersion liquid in which the base particles are dispersed is adjusted to a pH at which condensation of the organosilicon compound is difficult to proceed. Next, the organosilicon compound is hydrolyzed in another container and added to the mother particle dispersion liquid. After thoroughly mixing the base particle dispersion and the hydrolyzed liquid of the organosilicon compound with stirring, the pH is adjusted to a level suitable for condensation and the organosilicon polymer is condensed at once to form a surface layer on the toner surface.

  The hydrolysis reaction carried out in a separate container can be carried out at an arbitrary temperature by adding an organosilicon compound to an aqueous medium for hydrolysis adjusted to an arbitrary pH. However, when the pH of the aqueous medium for hydrolysis is adjusted to 2.0 or more and 7.0 or less and the temperature is controlled to 10 ° C. or more and 60 ° C. or less, the hydrolysis reaction rate is high and It is preferable because the condensation reaction is difficult to proceed. In addition, the concentration of the organosilicon compound in the aqueous medium for hydrolysis is preferably 1.0% by mass or more and 70.0% by mass or less from the same viewpoint. When the aqueous medium for hydrolysis and the organic silicon compound are phase-separated, it is preferable to carry out the hydrolysis reaction with stirring by a known method from the viewpoint of accelerating the reaction.

  The condensation in the toner base particle dispersion liquid can be performed at any pH and temperature. However, it is preferable to adjust the pH to 6.0 or more and 12.0 or less and to control the temperature to 30 ° C. or more and 100 ° C. or less because the condensation reaction proceeds rapidly.

  By the above method, it is considered that the surface layer containing the organosilicon polymer becomes uneven and a network is formed even between the convexes, so that the matrix is less likely to be exposed and the interparticle force can be reduced. In addition, it is considered that the variation in the surface potential distribution can be reduced by diffusing the localized charge generated in the toner throughout the toner due to the network structure between the formed protrusions.

  When the surface layer containing the organosilicon polymer is used, the content of the organosilicon polymer in the toner particles is preferably 0.5% by mass or more and 5.0% by mass or less. When the content is within the above range, the mechanical strength of the toner is improved, and the cracking or crushing of the toner can be suppressed, so that the generation of the toner fusion product in the developing device which is the starting point of the development streak can be suppressed. When the charge amount of the toner increases in a low temperature and low humidity environment, a strong electrostatic attractive force is generated between the toner fusion product and the toner without cracking or crushing, and further, the force between the two particles of the toner is within the above range. As a result, the pressure applied between the toner that is not cracked or crushed and the toner fusion product is reduced. As a result, it is possible to suppress the growth of the fused material caused by the toner adhering to the toner fused material one after another, and thus it is possible to greatly improve the development streak generated in the low temperature and low humidity environment. The content of the organosilicon polymer should be controlled by the type and amount of the organosilicon compound used for forming the organosilicon polymer, the method for producing toner particles during the formation of the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH. You can The method for measuring the content of the organosilicon polymer will be described later.

The organosilicon polymer is preferably a polymer having a partial structure represented by the following formula (R ^a T3).
^Ra- SiO _3/2 ( ^Ra T3)
(In the formula, R ^a represents a hydrocarbon group having 1 to 6 carbon atoms, an aryl group, or a structure represented by the following formula (i) or formula (ii).

（式（ｉ）および（ｉｉ）において、＊はＲ^aＴ３構造中のＳｉ元素との結合部位を表し、式（ｉｉ）におけるＬは、アルキレン基またはアリーレン基を表す。）

(In the formulas (i) and (ii), * represents a bonding site with the Si element in the R ^a T3 structure, and L in the formula (ii) represents an alkylene group or an arylene group.)

Regarding the four valences of the Si atoms in the above formula (R ^a T3), one is bound to R ^a and the remaining three are bound to O atoms. Each of the O atoms has a valence of 2 and is bonded to Si, that is, a siloxane bond (Si-O-Si). Considering Si atoms and O atoms as the organosilicon polymer, two Si atoms have three O atoms, and thus they are expressed as —SiO _3/2 .

The presence of the siloxane-based polymer portion —SiO _{3/2 in} the formula (R ^a T3) can be confirmed by measuring ²⁹ Si-NMR of the tetrahydrofuran insoluble matter in the toner particles. The presence of the vinyl polymer portion represented by the formulas (i) and (ii) can be confirmed by ¹³ C-NMR measurement of the tetrahydrofuran insoluble matter in the toner particles.

In the toner of the present invention, in the chart obtained by the ²⁹ Si-NMR measurement of the tetrahydrofuran (THF) insoluble matter of the toner particles, the peak attributed to the structure of the formula (R ^a T3) with respect to the total peak area of the organosilicon polymer is shown. The area ratio is preferably 20% or more.

A detailed measuring method will be described later, but this means that the organosilicon polymer contained in the toner particles has a partial structure represented by ^Ra- SiO3 _{/ 2} of 20% or more. There is. As described above, it is the meaning of the partial structure of —SiO _3/2 that three of the four valences of Si atoms are bonded to oxygen atoms and these oxygen atoms are bonded to another Si atom. If one of the oxygen atoms is a silanol group, the partial structure of the organosilicon polymer is represented by ^Ra- SiO2 _{/ 2-} OH. Furthermore, if two oxygen atoms are silanol groups, the partial structure will be ^Ra- SiO1 _{/ 2} (-OH) ₂ . Comparing these structures, it is closer to the silica structure represented by SiO ₂ that more oxygen atoms form a crosslinked structure with Si atoms. Therefore, the larger the number of —SiO _3/2 skeletons, the lower the surface free energy of the surface of the toner particles, and the more excellent the environmental stability and the contamination resistance of the members are. On the other hand, as the number of —SiO _3/2 skeletons decreases, the number of silanol groups having a strong negative charging property increases, and charge-up may not be completely suppressed. From the viewpoint of charging property and durability, it is preferably 100% or less, and more preferably 40% or more and 80% or less.

  The ratio of the peak area of the partial structure is the type and amount of the organosilicon compound used for forming the organosilicon polymer, and the reaction temperature, reaction time, and reaction of the hydrolysis, addition polymerization, and condensation polymerization during the organosilicon polymer formation. It can be controlled by the solvent and pH.

When a surface layer containing an organosilicon polymer is used, a backscattered electron image of the surface of the toner particles of 1.5 μm square is obtained by scanning electron microscope observation of the surface of the toner particles, and the backscattered electron image shows 256 floors. When a luminance histogram based on the number of pixels in which the abscissa of the gray scale is taken as the horizontal axis, the histogram has two maximum values P1 and P2 and a minimum value V between the P1 and P2, and the P2 is the organic value. It is a maximum value derived from a silicon polymer, the brightness of P1 is 20 or more and 70 or less, the brightness of P2 is 130 or more and 230 or less, and the number of pixels of P1 and P2 with respect to the total number of pixels of the backscattered electron image is Each of the proportions is 0.50% or more, and the total number of pixels having a luminance of 0 or more (Vl-30) or less is A1 and a luminance (Vl-29) or more with reference to the luminance Vl of V. Vl + 29) following total number of pixels of the AV, when the luminance (vl + 30) and 255 of the total number of pixels was A2, and more preferably satisfies the following formula (1) and (2).
(A1 / AV) ≧ 1.50 (1)
(A2 / AV) ≧ 1.50 (2)

  As will be described later, the acquisition condition of the backscattered electron image 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 formula are approximately several tens nm.

  In the present invention, in the scanning electron microscope observation of the surface of the toner particle having the surface layer containing the organosilicon polymer, a backscattered electron image of the surface of the toner particle of 1.5 μm square is obtained, and 256 gradations are obtained from the backscattered electron image. When a luminance histogram based on the number of pixels in which the horizontal axis is the luminance of the above is obtained, it is essential that the histogram has two maximum values P1 and P2 and a minimum value V between the P1 and P2.

  In the brightness histogram, lower brightness is darker (black) and higher brightness is brighter (white). A backscattered electron image obtained from a scanning electron microscope is also called a "composition image". The smaller the atomic number is, the darker the image is. Since the toner particles have an organosilicon polymer on the surface, the maximum value P1 with low brightness is derived from the base of the toner particles, and the maximum value P2 with high brightness is derived from the organosilicon polymer.

  The matrix here refers to a composition containing carbon as a main component such as a binder resin and a release agent contained in the toner particles. Further, the fact that P2 is derived from the organosilicon polymer can be confirmed by superimposing the backscattered electron image and the element mapping image by energy dispersive X-ray analysis (EDS) that can be obtained by scanning electron microscope observation. One of the requirements of the present invention is a bimodal histogram having P1 derived from the base of the toner particles, P2 derived from the organosilicon polymer, and the minimum value V between P1 and P2.

  It is also important that the brightness of P1 is 20 or more and 70 or less and the brightness of P2 is 130 or more and 230 or less. When the luminances of P1 and P2 are apart from each other 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 P1 do not overlap each other, and the separation is small. It will be good.

  As described above, P1 is derived from the toner particle matrix and P2 is derived from the organosilicon polymer. When the separation of peaks 1 and 2 is good, the matrix of the toner particles and the organosilicon polymer are efficiently localized on the surface of the toner particles, and the respective functions described below are more effectively exhibited. The brightness of P1 is preferably 20 or more and 60 or less, and the brightness of P2 is preferably 140 or more and 230 or less.

Further, it is necessary that the ratio of the number of pixels of P1 and P2 to the total number of pixels of the backscattered electron image is 0.50% or more. Further, with reference to the brightness Vl of the minimum value V, the total number of pixels of brightness 0 or more (Vl-30) or less is A1, the total number of pixels of brightness (Vl-29) or more (Vl + 29) or less is AV, and the brightness (Vl + 30). Assuming that the total number of pixels of 255 or more and 255 or less is A2, the following equations (1) and (2)
(A1 / AV) ≧ 1.50 (1)
(A2 / AV) ≧ 1.50 (2)
Satisfying is one of the requirements. Here, the number of pixels A1 having a luminance of 0 or more (Vl-30) or less is mainly composed of peak 1 having a maximum value of P1, and the number of pixels A2 having a luminance of (Vl + 30) or more and 255 or less has P2 as a maximum value. The peak 2 is the main component. As described above, since P1 is derived from the toner particle matrix and P2 is derived from the organosilicon polymer, each pixel contained in A1 belongs to the toner particle matrix, and each pixel contained in A2 belongs to the organosilicon polymer. To be done.

  That is, it is shown that as P1 is larger and A1 is larger, the base component is sufficiently present, and as P2 is larger and A2 is larger, the organosilicon polymer component is sufficiently present on the toner particle surface. As a result, the coefficient of variation between the two-particle force and the surface potential distribution falls within the above range, and the low temperature fixability becomes good.

Particularly preferable conditions are that the number of pixels of P1 and P2 is 0.70% or more and 5.00% or less with respect to the total number of pixels of the backscattered electron image, respectively, and the following formulas (3) and (4)
4.00 ≧ (A1 / AV) ≧ 1.70 (3)
4.00 ≧ (A2 / AV) ≧ 1.70 (4)
Is to meet.

  The brightness and the number of pixels of P1 and P2, the brightness Vl of the minimum value V, and the numbers of pixels A1, A2, and AV are the monomer species of the organosilicon polymer, the reaction temperature and the reaction time when the organosilicon polymer is formed, It can be controlled by the reaction solvent and pH.

  As a typical production example of the organosilicon polymer that can be used in the present invention, a method called a sol-gel method can be mentioned. The sol-gel method is a method in which a liquid raw material is used as a starting material, and is hydrolyzed and condensation-polymerized to form a gel through a sol state. It is used in a method for synthesizing glass, ceramics, an organic-inorganic hybrid, and a nanocomposite. By using this manufacturing method, it is possible to manufacture functional materials having various shapes such as surface layers, fibers, bulk bodies, and fine particles from a liquid phase at a low temperature.

  Specifically, the organosilicon polymer present in the surface layer of the toner particles is preferably produced by hydrolysis and polycondensation of a silicon compound represented by alkoxysilane.

  By providing the toner particles with a surface layer containing the organosilicon polymer, environmental stability is improved, and it is possible to obtain a toner having excellent storage stability, which is unlikely to cause deterioration in toner performance during long-term use. ..

  Furthermore, since the sol-gel method starts from a liquid and forms the material by gelling the liquid, various fine structures and shapes can be formed. In particular, when the toner particles are manufactured in an aqueous medium, the hydrophilicity of a hydrophilic group such as a silanol group of the organosilicon compound facilitates precipitation on the surface of the toner particles. The fine structure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH and the kind and amount of the organometallic compound.

  The organosilicon polymer in the present invention is preferably a product obtained by polycondensing an organosilicon compound having a structure represented by the following formula (Z).

（式（Ｚ）中、Ｒ₁は、炭素数が１以上６以下の炭化水素基、アリール基、又は下記式（ｉ）あるいは式（ｉｉ）で表される構造を表し、Ｒ₂、Ｒ₃及びＲ₄は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、アセトキシ基、又は、アルコキシ基を表す。）

(In the formula (Z), R ₁ represents a hydrocarbon group having 1 to 6 carbon atoms, an aryl group, or a structure represented by the following formula (i) or formula (ii), and R ₂ , R ₃ And R ₄ each independently represents a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group.)

（式（ｉ）および（ｉｉ）において、＊はＺ構造中のＳｉ元素との結合部位を表し、式（ｉｉ）におけるＬは、アルキレン基またはアリーレン基を表す。）

(In formulas (i) and (ii), * represents a bonding site with the Si element in the Z structure, and L in formula (ii) represents an alkylene group or an arylene group.)

The hydrocarbon group of R ₁ can improve the hydrophobicity, and toner particles having excellent environmental stability can be obtained. Further, an aryl group which is an aromatic hydrocarbon group, for example, a phenyl group can be used as the hydrocarbon group. When R ₁ has a large hydrophobicity, the charge amount tends to be large in various environments. Therefore, R ₁ is more preferably a hydrocarbon group having 1 to 3 carbon atoms in view of environmental stability. ..

R ₂ , R ₃ and R ₄ 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 polycondensed to form a crosslinked structure, and a toner excellent in member contamination resistance and development durability can be obtained. From the viewpoints of mild hydrolyzability at room temperature, deposition on the surface of the toner particles and coverage, an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The hydrolysis, addition polymerization and condensation polymerization of R ₂ , R ₃ and R ₄ can be controlled by the reaction temperature, reaction time, reaction solvent and pH.

In order to obtain the organosilicon polymer used in the present invention, an organosilicon compound having _three reactive groups (R ₂ , R ₃ and R ₄ ) in one molecule excluding R ₁ in the above formula (Z) is used. (Hereinafter, also referred to as trifunctional silane) may be used alone or in combination of two or more.

  The following is mentioned as said formula (Z). Vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyl Triacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxy Hydroxysilane, vinyl ethoxy methoxy hydroxy sila , Vinyldiethoxyhydroxysilane, trifunctional vinylsilane; allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, allylethoxydimethoxysilane, allyltrichlorosilane, allylmethoxydichlorosilane, allylethoxydichlorosilane, Allyldimethoxychlorosilane, Allylmethoxyethoxychlorosilane, Allyldiethoxychlorosilane, Allyltriacetoxysilane, Allyldiacetoxymethoxysilane, Allyldiacetoxyethoxysilane, Allylacetoxydimethoxysilane, Allylacetoxymethoxyethoxysilane, Allylacetoxydiethoxysilane, Allyltri Hydroxysilane, allylmethoxydihydroxysilane, allylethoxydihydroxysilane, Trifunctional allylsilanes such as rudimethoxyhydroxysilane, allylethoxymethoxyhydroxysilane, allyldiethoxyhydroxysilane; p-styryltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxy Dimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxy Dimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, Trifunctional methylsilanes such as methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane and methyldiethoxyhydroxysilane; ethyltrimethoxysilane, ethyltriethoxysilane, Trifunctional ethylsilane such as ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane; trifunctional such as propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane. Propylsilane; Butyltrimethoxysilane, Butyltriethoxysilane, Butyltrichlorosilane, Butyltriacetoxy Trifunctional butylsilanes such as orchid, butyltrihydroxysilane; hexylsilanes such as hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane; Trifunctional phenylsilanes such as methoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane. The organosilicon compounds may be used alone or in combination of two or more.

  As a result of the hydrolysis polycondensation, the content of the organosilicon compound satisfying the formula (Z) is preferably 50 mol% or more, more preferably 60 mol% or more in the organosilicon polymer.

  As a result of hydrolysis polycondensation, an organosilicon compound having the structure of the formula (Z), an organosilicon compound having four reactive groups in one molecule (tetrafunctional silane), and three reactions in one molecule. Group-containing organosilicon compound (trifunctional silane), organosilicon compound having two reactive groups in one molecule (difunctional silane) or organosilicon compound having one reactive group (monofunctional silane) in combination You may use the organosilicon polymer obtained by doing. Examples of the organosilicon compound that may be used in combination include the following. 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-aminopropyltriemethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (ami) Ethyl) -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) ) Trifluoroacetamide, trimethylsilyl trifluoromethanesulfonate, 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane, trimethylsilylacetylene, hexamethyldisilane, 3-isocyanatopropyltriethoxysilane, tetraisocyanatesilane, methyl Triisocyanate silane, vinyl triisocyanate silane.

  In the present invention, it is preferable that the surface layer containing the organosilicon polymer and the base portion are in contact with each other without any space. As a result, the occurrence of bleeding due to the resin component or the release agent inside the surface of the toner particles is suppressed, and a toner having excellent storage stability, environmental stability, and development durability can be obtained.

  In addition to the above organosilicon polymer, the surface layer may contain a resin such as a styrene-acrylic copolymer resin, a polyester resin or a urethane resin, and various additives.

  Hereinafter, specific toner manufacturing methods will be described, but the present invention is not limited thereto.

  As the first production method, after obtaining the toner base particles, the toner base particles are dispersed in an aqueous medium, and an organic silicon compound is added to the toner base particle dispersion liquid for condensation, and then the aqueous medium is removed to remove the toner particles. Is the way to get.

Hereinafter, an example of a method for producing toner base particles will be described.
(1) Suspension polymerization method: A polymerizable monomer composition containing a polymerizable monomer capable of forming a binder resin, a release agent, and optionally a colorant is granulated in an aqueous medium. Then, the toner base particles are obtained by polymerizing the polymerizable monomer.
(2) Grinding method: Toner base particles are obtained by melt-kneading a binder resin, a release agent, and optionally a colorant, and grinding.
(3) Dissolution suspension method: A binder resin, a release agent, and optionally a coloring agent are dissolved in an organic solvent to produce an organic phase dispersion liquid, which 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: Binder resin particles, release agent particles, and optionally particles such as a colorant are aggregated in an aqueous medium and associated to obtain toner base particles.

  The second production method is a polymerizable monomer composition capable of forming a binder resin, an organic silicon compound, a release agent, and a polymerizable monomer composition containing a colorant and the like in an aqueous medium. It is a method of obtaining toner particles by granulating and polymerizing the polymerizable monomer.

  As the third production method, a binder resin, an organic silicon compound, a release agent, and optionally a coloring agent are dissolved / dispersed in an organic solvent to produce an organic phase dispersion liquid, which is suspended in an aqueous medium. The method is to obtain toner particles by removing the organic solvent after granulation and polymerization.

  The fourth production method is a method in which binder resin particles, sol- or gel-state organosilicon compound-containing particles, and optionally colorant particles are aggregated in an aqueous medium and associated to form toner particles. ..

  The following are examples of the aqueous medium. Water; a mixed solvent of water and alcohols such as methanol, ethanol, propanol; and the like.

  Among the above-mentioned manufacturing methods, the method of manufacturing the toner base particles by the suspension polymerization method is the most preferable as the method for manufacturing the toner particles. In the suspension polymerization method, the organosilicon polymer is likely to be uniformly deposited on the surface of the toner particles, and localized charges on the toner surface are less likely to occur, so that the transfer dust, which is the effect of the present invention, is improved. The suspension polymerization method will be further described below.

  Other resins may be added to the polymerizable monomer composition, if necessary. Further, after the completion of the polymerization step, the produced particles are washed, collected by 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 distill off a part of the dispersion medium from the reaction system in the latter half of the polymerization step or after the completion of the polymerization step. After the completion of the polymerization step, the surface layer containing the organosilicon polymer may be formed using the mother particle dispersion liquid in which the toner mother particles are dispersed, without performing washing, filtration and drying.

  Next, the components contained in the toner will be described. The toner particles having the organic silicon polymer on the surface contain a binder resin, a release agent, a colorant as required, and other components.

[Binder resin]
The binder resin is not particularly limited, and conventionally known ones can be used. Preferable examples of the binder resin include vinyl resins and polyester resins. Examples of vinyl resins, polyester resins, and other binder resins include the following resins and polymers.

  Polystyrene, homopolymers of styrene such as polyvinyltoluene and its substitution products; 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-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Coalesced, styrene-pig Styrene-based 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, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These binder resins may be used alone or in combination.

  In the present invention, the binder resin preferably contains a carboxyl group from the viewpoint of chargeability, and is preferably a resin produced using a polymerizable monomer containing a carboxyl group. For example, (meth) acrylic acid such as α-ethylacrylic acid and crotonic acid, and α-alkyl derivative or β-alkyl derivative; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid and itaconic acid; monoacryloyl succinate Unsaturated dicarboxylic acid monoester derivatives such as oxyethyl ester, succinic acid monoacryloyloxyethylene ester, phthalic acid monoacryloyloxyethyl ester, and phthalic acid monomethacryloyloxyethyl ester.

  As the polyester resin, those obtained by polycondensing a carboxylic acid component and an alcohol component listed below can be used. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of alcohol components include bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

  Further, the polyester resin may be a polyester resin containing a urea group. As for the polyester resin, it is preferable not to cap the carboxyl groups such as terminals.

  In the toner of the present invention, the resin may have a polymerizable functional group for the purpose of improving the viscosity change of the toner at high temperature. Examples of the polymerizable functional group include a vinyl group, an isocyanate group, an epoxy group, an amino group, a carboxanxyl group, and a hydroxy group.

[Crosslinking agent]
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.

  For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 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 above acrylates What changed to methacrylate.

  The addition amount of the crosslinking agent is preferably 0.001 mass% or more and 15.000 mass% or less with respect to the polymerizable monomer.

[Release agent]
In the present invention, it is preferable to contain a release agent as one of the materials constituting the toner particles. Examples of the releasing agent usable for the toner particles include paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and its derivatives, montan wax and its derivatives, hydrocarbon wax and its derivatives by Fischer-Tropsch method, polyethylene, Polyolefin wax and its derivatives such as polypropylene, natural wax and its derivatives such as carnauba wax and candelilla wax, fatty acids such as higher aliphatic alcohol, stearic acid and palmitic acid, or their compounds, acid amide wax, ester wax , Ketones, hydrogenated castor oil and its derivatives, vegetable waxes, animal waxes, and silicone resins. The derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. The content of the release agent is preferably 5.0 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer.

[Colorant]
The toner of the present invention contains a colorant. The colorant is not particularly limited and, for example, the following known ones can be used.

  Examples of yellow pigments include condensed azo compounds such as 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, 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.

  The orange pigment includes the following.

  Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Benzidine Orange G, Induslen Brilliant Orange RK, Induslen Brilliant Orange GK.

  Examples of red pigments include condensation of red iron oxide, permanent red 4R, resole red, pyrazolone red, watching red calcium salt, lake red C, lake D, brilliant carmine 6B, brillant carmine 3B, eosin lake, rhodamine lake B, and alizarin lake. Examples thereof include azo compounds, diketopyrrolopyrrole compounds, anthraquinones, 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.

  Examples of blue pigments include copper phthalocyanine compounds and their derivatives such as alkali blue lake, Victoria blue lake, phthalocyanine blue, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, and indanthrene blue BG, anthraquinone compounds, and 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 green pigments include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of the white pigment 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 yellow colorant, the red colorant, and the blue colorant which are toned in black. These colorants can be used alone or in a mixture, and can be used in the state of a solid solution.

  Further, depending on the toner manufacturing method, it is necessary to pay attention to the polymerization inhibitory property and the dispersion medium migration property of the colorant. If necessary, the surface of the colorant may be surface-modified with a substance that does not inhibit polymerization. In particular, since many dyes and carbon black have a polymerization inhibiting property, caution is required when using them.

  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 100.0 parts by mass of the binder resin or the polymerizable monomer.

[Charge control agent]
In the present invention, the toner particles may contain a charge control agent. Known charge control agents can be used. In particular, a charge control agent having a high charging speed and capable of stably maintaining a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially no solubilized product in an aqueous medium is particularly preferable.

  Examples of the charge control agent that controls the toner particles to be negatively charged include the following.

  As an organometallic compound and a chelate compound, a monoazo metal compound, an acetylacetone metal compound, an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an oxycarboxylic acid and a dicarboxylic acid type metal compound. Others include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides or esters, and phenol derivatives such as bisphenol. Furthermore, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, and calixarene are mentioned.

  On the other hand, examples of the charge control agent that controls the toner particles to be positively charged include the following.

  Nigrosine modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and these Onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and lake pigments thereof (as lakers, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; resin-based charge control agents.

  These charge control agents may be contained alone or in combination of two or more. The addition amount of these charge control agents is preferably 0.01 parts by mass or more and 10.00 parts by mass or less with respect to 100.00 parts by mass of the binder resin.

[External additive]
The toner particles of the present invention can constitute the toner of the present invention without external addition, but in order to improve fluidity, chargeability, cleaning property, etc., so-called external additives such as fluidizing agent and cleaning agent are used. The toner of the present invention may be constituted by adding an auxiliary agent or the like.

Examples of the external additive include inorganic oxide fine particles such as silica fine particles, alumina fine particles and titanium oxide fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, or strontium titanate and titanium. Examples thereof include inorganic titanate compound fine particles such as zinc oxide. These may be used alone or in combination of two or more. It is preferable that these inorganic fine particles are subjected to a gloss treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil or the like in order to improve heat resistant storage stability and environmental stability. The BET specific surface area of the external additive is preferably 10 m ² / g or more and 450 m ² / g or less.

The BET specific surface area can be determined by the low temperature gas adsorption method by the dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, by using a specific surface area measuring device (trade name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the surface of the sample, and measurement is performed using the BET multipoint method. The BET specific surface area (m ² / g) can be calculated.

  The total amount of these various external additives added is 0.05 parts by mass or more and 5.0 parts by mass or less, preferably 0.1 parts by mass or more and 3.0 parts by mass, relative to 100.0 parts by mass of the toner. It is considered to be a part or less. Further, various external additives may be used in combination.

[Developer]
The toner of the present invention may be used as a magnetic or non-magnetic one-component developer, or may be mixed with a carrier and used as a two-component developer.

  As the carrier, for example, magnetic particles composed of conventionally known materials such as metals such as iron, ferrite, and magnetite, alloys of those metals with aluminum, and metals such as lead can be used. Among these, ferrite particles can be used. Is preferably used. Further, as the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a resin dispersion type carrier in which fine magnetic powder is dispersed in a binder resin, or the like may be used.

  The carrier preferably has a volume average particle size of 15 μm or more and 100 μm or less, more preferably 25 μm or more and 80 μm or less.

[About manufacturing method of toner particles]
As a method for producing the toner particles of the present invention, known means can be used, and a kneading pulverization method or a wet production method can be used. From the viewpoint of making the particle diameter uniform and controlling the shape, the wet production method can be preferably used. Further, examples of the wet manufacturing method include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method.

  Here, the suspension polymerization method will be described. In the suspension polymerization method, first, a polymerizable monomer for synthesizing a binder resin, a colorant and a salicylic acid-based resin are uniformly dissolved or dispersed using a ball mill or a disperser such as an ultrasonic disperser. The polymerizable monomer composition is prepared (step of preparing the polymerizable monomer composition). At this time, if necessary, a polyfunctional monomer, a chain transfer agent, a wax as a release agent, a charge control agent, a plasticizer, etc. can be appropriately added. Suitable examples of the polymerizable monomer in the suspension polymerization method include the vinyl-based polymerizable monomers shown below. 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-octyl, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and 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-nonyl Acrylic polymerizable monomers such as 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-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethylphos Fate ethyl methacrylate, dibutyl phosphate ethyl ester Methacrylic polymerizable monomers such as acrylates; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl esters such as vinyl formate; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.

  Next, the polymerizable monomer composition is put into an aqueous medium prepared in advance, and a droplet made of the polymerizable monomer composition is desired by a stirrer or a disperser having a high shearing force. To the size of the toner particles (granulating step).

  It is preferable that the aqueous medium in the granulation step contains a dispersion stabilizer in order to control the particle size of the toner particles, sharpen the particle size distribution, and suppress coalescence of the toner particles in the manufacturing process. The dispersion stabilizer is generally classified into a polymer that exhibits a repulsive force due to steric hindrance and a poorly water-soluble inorganic compound that stabilizes the dispersion by electrostatic repulsive force. Since the fine particles of the poorly water-soluble inorganic compound are dissolved by an acid or an alkali, they can be easily dissolved and removed by washing with an acid or an alkali after the polymerization, and thus are preferably used.

  As the dispersion stabilizer of the poorly water-soluble inorganic compound, those containing any of magnesium, calcium, barium, zinc, aluminum and phosphorus are preferably used. More preferably, it is desired to contain any of magnesium, calcium, aluminum and phosphorus. Specifically, the following are mentioned.

  Magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, hydroxyapatide.

  An organic compound such as polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, or starch may be used in combination with the dispersion stabilizer. These dispersion stabilizers are preferably used in an amount of 0.01 part by mass or more and 2.00 parts by mass or less based on 100.00 parts by mass of the polymerizable monomer. Further, 0.001% by mass or more and 0.1% by mass or less of a surfactant may be used in combination for making the dispersion stabilizer finer. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate are preferably used.

  After the granulation step or while performing the granulation step, the temperature is generally set to 50 ° C. or higher and 90 ° C. or lower for polymerization to obtain a toner particle dispersion (polymerization step).

  In the polymerization step, the temperature of the treatment liquid has a great influence on the fixing performance of the toner particles, and therefore the stirring operation is generally performed so that the temperature distribution in the container becomes uniform. When the polymerization initiator is added, it can be carried out at any time and for a required time. In addition, the temperature may be raised in the latter half of the polymerization reaction for the purpose of obtaining a desired molecular weight distribution. After that, part of the aqueous medium may be distilled off by a distillation operation. The distillation operation can be performed under normal pressure or reduced pressure.

  As the polymerization initiator used in the suspension polymerization method, an oil-soluble initiator is generally used. For example, the following may be mentioned.

  2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4 An azo compound such as -methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert- Butyl peroxy-2-ethyl hexanoate, benzoyl peroxide, tert-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, te t- butyl hydroperoxide, di -tert- butyl peroxide, tert- butyl peroxypivalate, peroxide initiators such as cumene hydroperoxide.

  As the polymerization initiator, a water-soluble initiator may be used in combination, if necessary, and the following may be mentioned.

  Ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) Hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

  These polymerization initiators can be used alone or in combination, and in order to control the degree of polymerization of the polymerizable monomer, it is also possible to further add and use a chain transfer agent, a polymerization inhibitor or the like.

  The toner particles in the present invention preferably have a weight average particle diameter of 3.0 μm or more and 10.0 μm or less from the viewpoint of obtaining an image with high definition and high resolution. The weight average particle diameter of the toner can be measured by the pore electrical resistance method. For example, it can be measured by using "Coulter Counter Multisizer 3" (manufactured by Beckman Coulter, Inc.). The toner particle dispersion liquid thus obtained is sent to a filtration step for solid-liquid separating the toner particles and the aqueous medium.

  Solid-liquid separation for obtaining toner particles from the obtained toner particle dispersion liquid can be carried out by a general filtration method, and thereafter, in order to remove foreign substances that could not be completely removed from the toner particle surface, reslurry or washing water is used. Further washing is preferably carried out by washing with water. After sufficient washing is performed, solid-liquid separation is performed again to obtain a toner cake. After that, it is dried by a known drying means, and if necessary, a group of particles having a particle diameter outside the predetermined range is separated by classification to obtain toner particles. The particles having a particle size outside the predetermined range may be reused in order to improve the final yield.

  Hereinafter, various measuring methods related to the present invention will be described. When the organic fine powder or the inorganic fine powder is externally added to the toner, the sample obtained by removing the organic fine powder or the inorganic fine powder by the following method is used.

  160.0 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved with a water bath to prepare a concentrated sucrose solution. In a centrifuge tube (volume 50 ml), 31.0 g of the above concentrated sucrose solution and Contaminone N (a nonionic surfactant, anionic surfactant, organic builder, pH 7 precision measuring instrument for washing neutral) 6 mL of a 10 mass% aqueous solution of detergent, manufactured by Wako Pure Chemical Industries, Ltd. is added. 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 (available from AS-1N AS ONE 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.) under conditions of 3500 rpm and 30 minutes.

  By this operation, the toner particles and the external additive are separated. Visually confirm that the toner and the aqueous solution are sufficiently separated, and collect the toner separated in the uppermost layer with a spatula or the like. After filtering the collected toner with a vacuum filter, it is dried with a dryer for 1 hour or more to obtain a measurement sample. This operation is performed multiple times to secure the required amount.

<Measurement method of force between two particles>
The force between the two particles of the toner is measured using an Aggrobot manufactured by Hosokawa Micron Co., Ltd. according to the instruction of the apparatus.

  The specific measurement method and measurement conditions are as follows.

(Sample condition)
Powder loading mass: (for magnetic toner) 9.2 (g), (for non-magnetic toner) 7.7 (g)
Binder mass: 0 (g)
True density of powder: True density of toner (kg / m ³ ).
Liquid binder density: 0 (kg / m ³ )
Body area average diameter of powder: Weight average particle diameter of toner (D4) (μm)
Specific surface area shape factor: 6 (-)
Minimum porosity of dry powder: 0.26 (-)

(Measurement condition)
Environmental temperature: 25 ℃
Humidity: 50%
Cell inner diameter: 25 mm (see FIG. 1 (A))
Height inside cell: 37.5 mm (see FIG. 1 (A))
Cell temperature: 25 ° C
Spring wire diameter: 1.0 mm
Compression speed: 1.0 mm / sec
Compression holding time: 0.0sec
Compressive stress: 8kg / cm ²
Tensile speed: 0.40 mm / sec
Tensile sampling start time: 0.0 sec
Tensile sampling time: 25sec

(1) Magnetic toner In a 25 ° C./50% environment, 9.2 g of toner is filled in the cylindrical cell divided into upper and lower halves shown in FIG. Then, the compression rod is lowered at 1.0 mm / sec to apply a vertical load of 78.5 N to form a toner compact.

  Then, as shown in FIG. 2 (B), the maximum tensile rupture force obtained when the toner compact is broken by lifting the upper cell with a spring at a speed of 0.40 mm / sec and pulling the toner compact. To measure the interparticle force (nN).

(2) Non-Magnetic Toner In a 25 ° C./50% environment, 7.7 g of toner is filled in the cylindrical cell divided into upper and lower halves shown in FIG. Then, the compression rod is lowered at 1.0 mm / sec to apply a vertical load of 78.5 N to form a toner compact.

  Thereafter, as shown in FIG. 1B, the upper cell is lifted by a spring at a speed of 0.40 mm / sec to pull the toner compact, and the maximum tensile breaking force obtained when the toner compact is broken. To measure the interparticle force (nN).

<Calculation method of coefficient of variation of surface potential distribution>
The coefficient of variation of the surface potential distribution inside the toner particles was calculated from the surface potential distribution measured with a Kelvin probe force microscope (KPFM).

The apparatus and observation conditions of KPFM are as follows.
Device used: Bruker Japan KK Dimension Icon AFM
Probe: SCM-PtSi
Measurement mode: Peak force tapping potential feedback method: FM method Scan size: 2.0 μm × 2.0 μm
Scan rate: 0.5Hz
Resolution: 256 x 256
Set point: 10nN

  In a normal temperature and normal humidity environment (25 ° C./50% RH), 1.0 g of toner and 19.0 g of magnetic carrier N-01 (manufactured by Japan Imaging Society) are put in a 50 mL plastic bottle with a lid and left for 24 hours. Then, a two-component developer was prepared by shaking with a shaker (YS-LD: manufactured by Yayoi Co., Ltd.) at a speed of 4 reciprocations per second for 5 minutes.

  The two-component developer is sprinkled on the medicine packing paper, and a magnet is applied from the back side of the medicine packing paper to fix the two-component developer on the medicine packing paper. A carbon tape was attached to a stainless steel sample stand, and toner particles were transferred from the two-component developer to the carbon tape to prepare a measurement sample for KPFM.

  The measurement area is near the apex where the toner particles have the smallest curvature, and the measurement is performed with a scan size of 2.0 μm × 2.0 μm.

  The measurement mode is a peak force tapping mode (a measurement mode that scans the probe with a sine wave and separates the probe when the contact pressure becomes constant), in which the surface potential of the toner particle is not affected by the measurement by contacting the toner particles with a small force. Using. The high-resolution surface potential distribution of the toner particles was measured in the measurement mode.

  The surface potential was measured by KPFM at each point with a resolution of 256 × 256. The surface potential average value was calculated by averaging the potentials at each point with a resolution of 256 × 256. The coefficient of variation of the surface potential distribution was calculated by dividing the standard deviation obtained from the surface potential of each of the above measurement points by the absolute value of the average value.

  The above procedure was performed for 10 toner particles, and the average value of each was used as the physical property value of the toner obtained from the surface potential distribution.

<Measurement of Organosilicon Polymer Amount in Toner>
The amount of organosilicon polymer in the toner was measured by the following method.

  The amount of the organosilicon polymer is measured by a wavelength dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and attached dedicated software "SuperQ ver. 4.0F" for setting measurement conditions and analyzing measurement data. (Manufactured by PANalytical) is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. When measuring a light element, a proportional counter (PC) is used, and when measuring a heavy element, a scintillation counter (SC) is used.

  As a measurement sample, 4 g of toner particles were placed in a dedicated press aluminum ring and flattened, and a tablet molding compressor "BRE-32" (manufactured by Maekawa Test Machine Co., Ltd.) was used, and the pressure was 60 at 20 MPa. Pellets that are pressed for 2 seconds and molded into a thickness of 2 mm and a diameter of 39 mm are used.

To 100.0 parts by mass of toner particles not containing an organosilicon polymer, 0.5 parts by mass of silica (SiO ₂ ) fine powder was added instead of the organosilicon polymer, and a coffee mill was used. Mix well. Similarly, fine silica powder is mixed with toner particles in an amount of 5.0 parts by mass and 10.0 parts by mass, and these are used as a sample for a calibration curve.

For each sample, pellets of the sample for the calibration curve were prepared as described above using the tablet molding compressor, and when PET was used for the dispersive crystal, it was observed at the diffraction angle (2θ) = 109.08 °. The Si-Kα ray count rate (unit: cps) is measured. At this time, the acceleration voltage and the current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the obtained X-ray count rate as the vertical axis and the addition amount of SiO ₂ in each calibration curve sample as the horizontal axis.

  Next, the toner to be analyzed is pelletized as described above by using a tablet molding compressor, and the count rate of the Si-Kα ray is measured. Then, the amount of organosilicon polymer in the toner is determined from the above calibration curve.

<Method for Confirming Partial Structure Represented by Formula (R ^a T3)>
In the present invention, the unit of the hydrocarbon group bonded to the silicon atom in the partial structure represented by the following formula (R ^a T3) was confirmed by ¹³ C-NMR (solid state) measurement. The measurement conditions and sample preparation method are shown below.
^Ra- SiO _3/2 ( ^Ra T3)
(In the formula, R ^a represents a hydrocarbon group having 1 to 6 carbon atoms, an aryl group, or a structure represented by the following formula (i) or formula (ii).

（式（ｉ）および（ｉｉ）において、＊はＲ^aＴ３構造中のＳｉ元素との結合部位を表し、式（ｉｉ）におけるＬは、アルキレン基またはアリーレン基を表す。）

(In the formulas (i) and (ii), * represents a bonding site with the Si element in the R ^a T3 structure, and L in the formula (ii) represents an alkylene group or an arylene group.)

" ¹³ C-NMR (solid) measurement conditions"
Device: JEOL RESONANCE JNM-ECX500II
Sample tube: 3.2 mmφ
Sample: Tetrahydrofuran insoluble matter of toner particles for NMR measurement (preparation method is 150 mg)
Measurement temperature: Room temperature Pulse mode: CP / MAS
Measurement nuclear frequency: 123.25MHz ( ^13C )
Reference substance: Adamantane (external standard: 29.5 ppm)
Sample rotation speed: 20 kHz
Contact time: 2ms
Delay time: 2s
Total number of times: 1024

"Sample preparation method"
Preparation of measurement sample: 10.0 g of toner particles are weighed and put into a cylindrical filter paper (No. 86R manufactured by Toyo Roshi Kaisha, Ltd.), put on a Soxhlet extractor, and extracted with 200 ml of tetrahydrofuran as a solvent for 20 hours to obtain a filter cake 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.

  In the present invention, when the above-mentioned organic fine powder or inorganic fine powder is externally added to the toner, the organic fine powder or inorganic fine powder is removed by the following method to obtain toner particles.

  160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved with a water bath to prepare a concentrated sucrose solution. In a centrifuge tube, 31 g of the concentrated sucrose solution, and 10% by weight aqueous solution of a contaminone N (a nonionic surfactant, an anionic surfactant, an organic builder, a pH 7 precision measuring instrument cleaning neutral detergent), 6 mL of Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion liquid. To this dispersion, 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 at 350 spm (strokes per min) for 20 min. After shaking, the solution is replaced with a glass tube for swing rotor (50 mL), and separated by a centrifuge under the conditions of 3500 rpm and 30 min. By this operation, the toner particles and the detached external additive are separated. Visually confirm that the toner and the aqueous solution are sufficiently separated, and collect the toner separated in the uppermost layer 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 more to obtain toner particles. This operation is performed multiple times to secure the required amount.

In the above formula (R ^a T3), in the case where R ^a is the partial structure represented by the above formula (i), depending on the presence or absence of a signal resulting from the methine group (> CH—Si) bonded to the silicon atom, The presence of the partial structure represented by the formula (R ^a T3) was confirmed.

In the above formula (R ^a T3), when R ^a is a partial structure represented by the above formula (ii), a methylene group (Si—CH ₂ —) bonded to a silicon atom, an ethylene group (Si—C _2). The presence of the unit represented by the above formula (R ^a T3) is confirmed by the presence or absence of a signal resulting from an alkylene group such as H ₄ −) or an arylene group such as a phenylene group (Si—C ₆ H ₄ —). did.

In the above formula (R ^a T3), when R ^a is a partial structure represented by a hydrocarbon group having 1 to 6 carbon atoms and an aryl group, a methyl group (Si—CH ₃ ) bonded to a silicon atom. ), ethyl group (Si-C ₂ H _5), propyl (Si-C ₃ H _7), butyl group (Si-C ₄ H _9), pentyl groups (Si-C ₅ H _11), hexyl (Si -C ₆ H ₁₃₎ or an aryl group such as phenyl group (Si-C ₆ H ₅ - the presence or absence of signal caused etc.), confirmed the presence of the unit represented by the formula (R ^a T3).

<Method of acquiring backscattered electron image of toner particle surface>
The backscattered electron image of the surface of the toner particles was acquired by a scanning electron microscope (SEM). The SEM device and observation conditions are as follows.
Equipment used: ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd.
Accelerating voltage: 1.0 kV
WD: 2.0 mm
Aperture Size: 30.0 μm
Detection signal: EsB (energy selective reflection 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
Pre-treatment: Spraying toner particles on carbon tape (no vapor deposition)

  The contrast and brightness are determined according to the following procedure. First, on the luminance histogram, the two maximum values P1 and P2 each have the largest possible number of pixels, and the contrast is set so that the luminances of P1 and P2 are as far apart as possible. Next, the brightness is set so that the bottoms of the two peaks having the maximum values of P1 and P2 fall within the brightness histogram. These contrast and brightness are appropriately set in accordance with the above procedure according to the state of the apparatus used. Further, the accelerating 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 undeposited sample, and selective detection of backscattered electrons having high energy. .. 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>
The fact that P2 is derived from an organosilicon polymer was confirmed by superimposing the backscattered electron image and the element mapping image by energy dispersive X-ray analysis (EDS) that can be obtained with a scanning electron microscope (SEM).

The SEM / EDS apparatus and observation conditions are as follows.
Equipment used (SEM): ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd.
Equipment (EDS): Thermo Fisher Scientific Co., Ltd. NORAN System 7, Ultra Dry EDS Detector
Accelerating voltage: 5.0kV
WD: 7.0 mm
Aperture Size: 30.0 μm
Detection signal: SE2 (secondary electron)
Observation magnification: 50,000 times Mode: Spectral Imaging
Pretreatment: Toner particles are sprinkled on carbon tape and sputtered with platinum.

  The mapping image of the silicon element obtained by this method and the backscattered electron image are superposed, and it is confirmed that the silicon atom part of the mapping image and the bright part of the backscattered electron image match.

<How to obtain luminance histogram>
The brightness histogram is acquired by analyzing the backscattered electron image of the surface of the toner particles obtained by the above method, using the image processing software ImageJ (developed by Wayne Rashhand). The procedure is shown below.

  First, the backscattered electron image to be analyzed is converted into 8-bit from Type in the Image menu. Next, the median diameter is set to 2.0 pixels from Filters in the Process menu to reduce image noise. Estimate the image center after excluding the observation condition display area displayed at the bottom of the backscattered electron image, and select a range of 1.5 μm square from the center of the backscattered electron image using the rectangular tool (Rectangle Tool) on the toolbar. ..

  Next, select Histgram in the Analyze menu to display the luminance histogram in a new window. The value of the brightness histogram is acquired from List of the window. If necessary, the brightness histogram may be fitted. From this, the brightness and the number of pixels of the maximum values P1 and P2, the brightness Vl of the minimum value V, and the pixel numbers 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 used as the physical property value of the toner particles obtained from the luminance histogram.

<Method of measuring weight average particle diameter (D4) of toner particles>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precision particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by a pore electrical resistance method is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  The electrolytic aqueous solution used for the measurement may be prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).

  Before the measurement and analysis, the dedicated software was set as follows.

  On the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). Set the value obtained by using the product. The threshold and noise level are automatically set by pressing the "Threshold / noise level measurement button". In addition, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check is put in “Flash of aperture tube after measurement”.

  On 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 to 60 μm.

The specific measuring method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution was placed in a glass 250 ml round-bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the "aperture flush" function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is placed in a glass 100 ml flat-bottom beaker. In this, as a dispersant, "contaminone N" (a nonionic surfactant, an anionic surfactant, a 10 mass% aqueous solution of a neutral detergent for washing precision measuring instruments of pH 7 comprising an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.3 ml of a diluted solution is added.
(3) An ultrasonic disperser “Ultrasonic Dispersion System Tetra 150” (manufactured by Nikkaki Bios Co., Ltd.) having an electric output of 120 W is prepared by incorporating two oscillators having an oscillation frequency of 50 kHz with phases shifted by 180 degrees. About 3.3 liters of ion-exchanged water is put into the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to this 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 becomes maximum.
(5) About 10 mg of toner is added little by little to the electrolytic aqueous solution in a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C or higher and 40 ° C or lower.
(6) To the round-bottom beaker (1) installed in the sample stand, drop the toner-dispersed aqueous electrolyte solution (5) with a pipette, and adjust so that the measured concentration is about 5%. .. Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the apparatus to calculate the weight average particle diameter (D4). The “average diameter” on the “Analysis / volume statistical value (arithmetic mean)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” of each material are based on mass unless otherwise specified.

[Example 1]
(Preparation process of aqueous medium 1)
To 390.0 parts of ion-exchanged water in the reaction vessel, 14.0 parts of sodium phosphate (12 hydrate manufactured by Lhasa Kogyo Co., Ltd.) was charged, and the temperature 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, an aqueous calcium chloride solution prepared by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water was collected. Then, an aqueous medium containing the dispersion stabilizer was prepared. Furthermore, 10 mass% hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0, and thus an aqueous medium 1 was obtained.

(Process for preparing 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 further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5.0 hours, A pigment dispersion was prepared.

The following materials were added to the pigment dispersion.
-Styrene: 15.0 parts-n-butyl acrylate: 25.0 parts-Divinylbenzene (crosslinking agent): 0.3 parts-Saturated polyester resin: 4.0 parts (propylene oxide-modified bisphenol A (2 mol addition product) 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.): 9.0 parts These were kept warm at 65 ° C. 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.

(Preparation process of organic silicon compound aqueous solution)
60.0 parts of ion-exchanged water was weighed in a reaction vessel equipped with a stirrer and a thermometer, and the pH was adjusted to 3.0 using 10% by mass of hydrochloric acid. This was heated with stirring to bring the temperature to 70 ° C.

  Then, 40.0 parts of methyltriethoxysilane was added and stirred for 2 hours to hydrolyze the organosilicon compound for the surface layer. The end point of hydrolysis was visually confirmed to be one layer without separation of oil and water, and cooling was performed to obtain an organic silicon compound aqueous solution 1.

(Granulation process)
The temperature of the aqueous medium 1 is 70 ° C. K. While maintaining the rotation speed of the homomixer at 12000 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 9.0 parts of t-butylperoxypivalate as a polymerization initiator was added. Granulation was performed for 10 minutes while maintaining 12,000 rpm with the stirring device.

(Polymerization process)
After the granulation step, the stirrer was changed to a propeller stirring blade, polymerization was carried out for 5.0 hours at 70 ° C while stirring at 150 rpm, and the temperature was raised to 95 ° C and heated for 2.0 hours for polymerization. The reaction was performed to obtain a slurry of base particles.

  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 Hydrolyzate 1 of the organosilicon compound for the surface layer was added to start formation of the toner surface layer. After being kept as it was for 30 minutes, the slurry was adjusted to pH = 9.0 to complete the condensation by using an aqueous solution of sodium hydroxide and kept for another 300 minutes to form a surface layer.

(Washing and drying process)
After the completion of the polymerization process, the obtained toner slurry is cooled, hydrochloric acid is added to the toner slurry to adjust the pH to 1.5 or less, and the mixture is left to stir for 1 hour. Got a cake

  This was reslurried with ion-exchanged water to form a dispersion again, and then solid-liquid separation was performed with the above-mentioned filter. The reslurry and solid-liquid separation were repeated until the electric conductivity of the filtrate became 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 a flash dryer, a jet jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and fine coarse powder was cut using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1.

  The drying conditions were such that the blowing temperature was 90 ° C., the dryer outlet temperature was 40 ° C., and the toner cake supply rate was adjusted so that the outlet temperature did not deviate from 40 ° C. according to the water content of the toner cake.

  In this example, the obtained toner particles 1 were used as the toner 1 as they were without adding an external additive.

  It was confirmed by the method described above that Toner 1 has a surface layer containing an organosilicon polymer. Table 2 shows the physical properties of Toner 1 thus obtained. The evaluation method of Toner 1 will be described below. The results are shown in Table 3.

<Development evaluation of toner using laser beam printer>
A remodeled machine of a commercially available Canon laser beam printer "LBP7600C" was used.

  The modification point was set by changing the gear and software of the main body of the evaluation machine so that the number of rotations of the developing roller was rotated at twice the peripheral speed with respect to the drum. Toner cartridge of LBP7600C was loaded with 40 g of toner.

(1) Evaluation under low temperature and low humidity environment (solid followability, transfer dust, halftone reproducibility, development streak)
Under a low temperature and low humidity environment (15 ° C./10% RH), 5 solid images were output on LETTER size Business 4200 paper (75 g / m ² manufactured by XEROX).

  Further, a grid pattern having a thickness of 100 μm (thickness in the electrostatic latent image) at 1 cm intervals was output.

  Furthermore, one halftone image was output.

  After that, 2000 sheets of images with a print rate of 1% were output.

  After that, one halftone image was output.

  The obtained solid images, lattice pattern images, and halftone images were evaluated for solid followability, transfer dust, halftone reproducibility, and development streaks.

  In addition, the image density is measured by using a "Macbeth reflection densitometer RD918" (manufactured by Macbeth Co., Ltd.) and following the attached instruction manual to measure the relative density with respect to the image of the white background portion where the image density is 0.00. The relative density thus obtained was used as the image density value.

[Evaluation criteria]
(Solid followability)
Evaluation was made based on the difference between the image density of the leading edge of the first solid image and the image density of the trailing edge of the third solid image.
A: The difference between the image density of the leading edge of the first solid image and the image density of the trailing edge of the third solid image is less than 0.10 B: The image density of the leading edge of the first solid image and the entire solid The difference between the image density of the trailing edge of the third solid image is 0.10 or more and less than 0.20 C: The image density of the leading edge of the first solid image and the image density of the trailing edge of the third solid image The difference is 0.20 or more and less than 0.30 D: The difference between the image density of the leading edge of the first solid image and the image density of the trailing edge of the third solid image is 0.30 or more and less than 0.40 E: The difference between the image density of the leading edge of the first solid image and the image density of the trailing edge of the third solid image is 0.40 or more.

(Transfer dust)
The lattice pattern image was observed using a magnifying glass with a magnification of 25 times, and the transfer dust (a phenomenon in which toner is scattered around a character or line image) was evaluated based on the following criteria.
A: The line is very sharp and there is almost no transfer dust. B: The toner is slightly scattered and the line is sharp. C: The toner is slightly scattered, but the line is relatively sharp. D: The toner is scattered. Many, the lines have a hazy shape

(Halftone reproducibility)
A halftone image (49th gradation counted from a solid white image when solid white to solid black is divided into 256 gradations) is visually observed and the halftone reproducibility of the image is based on the following criteria. It evaluated based on.
A: It feels smooth and smooth.
B: I don't feel much rubbing.
C: There is a slight feeling of roughness.
D: There is a clear feeling of roughness.

(Development line)
The number of vertical stripes appearing on the developing roller and the halftone image was evaluated.
A: Vertical streaks in the paper discharge direction are not seen on the developing roller or on the image.
B: Five or less thin streaks in the circumferential direction are seen at both ends of the developing roller. Alternatively, only a few vertical stripes in the paper discharge direction can be seen on the image. However, it is a level that can be erased by image processing.
C: Six or more and 20 or less thin streaks in the circumferential direction are seen on both ends of the developing roller. Alternatively, some fine streaks can be seen on the image. A level that cannot be erased even with image processing.
D: 21 or more streaks are seen on the developing roller and on the image, and cannot be erased even by image processing.

(2) Evaluation under high temperature and high humidity environment (halftone reproducibility)
The process cartridge filled with the toner was stored for 3 days in a high temperature and high humidity environment (35 ° C./80% RH). After that, all solid images were output on five LETTER size Businesses 4200 sheets (XEROX, 75 g / m ² ).

  Then, one halftone image was output, and the halftone reproducibility was evaluated based on the same evaluation criteria as in (1).

(3) Evaluation under normal temperature and normal humidity environment (low temperature fixability)
Using LBP7600C modified so that the fixing temperature could be adjusted, the fixing temperature was changed from 140 ° C. in steps of 5 ° C. under a normal temperature and normal humidity environment (25 ° C./50% RH) at a process speed of 300 mm / sec. For the toner to be evaluated, a solid image with a toner loading of 0.40 mg / cm ² was formed on LETTER size Business 4200 paper (XEROX, 75 g / m ² ) and heated and pressed without oil to form a fixed image. Formed. Using Kimwipe (S-200, manufactured by Crecia Co., Ltd.), a load of 7.35 kPa (75 g / cm ² ) was applied, and the fixed image was rubbed 10 times, and the temperature at which the image density reduction rate before and after rubbing became less than 5% was measured. The fixing temperature was used and the evaluation was made based on the following criteria.

To measure the image density, a color reflection densitometer X-RITE 404A (manufactured by X-Rite Co.) was used, and the relative density to the printout image of the white background portion of the document density of 0.00 was measured, and after rubbing The reduction rate of image density 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

[Examples 2, 3, 13, 14]
Toner particles 1 produced in Example 1 were externally added as shown in Table 1 to produce toners 2, 3, 13 and 14. The method of external addition is to mix 100.0 parts of toner particles with the external additives in the number shown in Table 1 using a Mitsui Henschel mixer (Mitsui Miike Kakoki Co., Ltd.) at 3000 rpm for 15 minutes to obtain a toner. Obtained.

The titanium oxide fine particles in Table 1 were treated with 3,3,3-trifluoropropyltrimethoxysilane (6% by mass) and isobutyltrimethoxysilane (6% by mass), and had a BET specific surface area of 34 m ² / g. I used one.

  As the hydrotalcite fine particles in Table 1, DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd. was used.

  Physical properties of the obtained toner are shown in Table 2 and evaluation results are shown in Table 3.

[Examples 4 to 12, 15]
In Example 1, the type of the organosilicon compound used in the “organic silicon compound aqueous solution preparation step” and the addition number of the organosilicon compound aqueous solution 1 in the “polymerization step” were changed as shown in Table 1. Toners 4 to 12 and Toner 15 were produced in the same manner as in Example 1 except for the above.

  It was confirmed by the method described above that the obtained toner had a surface layer containing an organosilicon polymer. Table 2 shows the physical properties of the toner, and Table 3 shows the evaluation results.

[Comparative Example 1]
In Example 1, 15 parts of methyltriethoxysilane, which is an organosilicon compound, was added as a monomer in the “step of preparing a polymerizable monomer composition” instead of performing the “organic silicon compound aqueous solution preparation step”. did.

  Further, in the "polymerization step", the pH of the organic silicon compound aqueous solution was not added after the slurry of the base particles was obtained, and only the pH adjustment and the subsequent holding were performed.

  Toner particles 16 were produced in the same manner as in Example 1 except for the above. The toner particles 16 thus obtained were used as the toner 16 as they were without any external addition.

  It was confirmed by the method described above that the obtained toner had a surface layer containing an organosilicon polymer. Physical properties of the obtained toner are shown in Table 2 and evaluation results are shown in Table 3.

[Comparative Example 2]
In Example 1, 8 parts of methyltriethoxysilane of the organosilicon compound was added as a monomer in the "preparation step of the polymerizable monomer composition" instead of "the preparation step of the organosilicon compound aqueous solution was not performed. ..

  Further, in the "polymerization step", the pH of the organic silicon compound aqueous solution was not added after the slurry of the base particles was obtained, and only the pH adjustment and the subsequent holding were performed.

  Toner particles 17 were produced in the same manner as in Example 1 except for the above. The toner particles 17 obtained were used as the toner 17 as they were without external addition.

  It was confirmed by the method described above that the obtained toner had a surface layer containing an organosilicon polymer. Physical properties of the obtained toner are shown in Table 2 and evaluation results are shown in Table 3.

[Comparative Example 3]
In Example 1, 4 parts of methyltriethoxysilane of the organosilicon compound was added as a monomer in the “preparation step of the polymerizable monomer composition” instead of performing the “preparation step of the organosilicon compound aqueous solution”. did.

  Further, in the "polymerization step", the pH of the organic silicon compound aqueous solution was not added after the slurry of the base particles was obtained, and only the pH adjustment and the subsequent holding were performed.

  Toner particles 18 were prepared in the same manner as in Example 1 except for the above. The toner particles 18 thus obtained were used as the toner 18 as they were without external addition.

  It was confirmed by the method described above that the obtained toner had a surface layer containing an organosilicon polymer. Physical properties of the obtained toner are shown in Table 2 and evaluation results are shown in Table 3.

[Comparative Examples 4 to 6]
The toner particles 16 prepared in Comparative Example 1 were externally added as shown in Table 2 to prepare toners 19 to 21. The method of external addition is to mix 100.0 parts of toner particles with the external additives in the number shown in Table 1 using a Mitsui Henschel mixer (Mitsui Miike Kakoki Co., Ltd.) at 3000 rpm for 15 minutes to obtain a toner. Obtained.

The hydrophobic silica fine particles in Table 2 were those treated with silicone oil (20% by mass) and having a BET specific surface area of 170 m ² / g.

  Physical properties of the obtained toner are shown in Table 2 and evaluation results are shown in Table 3.

[Comparative Examples 7 and 8]
In Example 1, the "organic silicon compound aqueous solution preparation step" was not performed.

  Further, in the "polymerization step", the pH of the organic silicon compound aqueous solution was not added after the slurry of the base particles was obtained, and only the pH adjustment and the subsequent holding were performed. Toner particles 22 were produced in the same manner as in Example 1 except for the above.

  Externally added to the obtained toner particles as shown in Table 1, toners 22 and 23 were produced. The method of external addition is to mix 100.0 parts of toner particles with the external additives in the number shown in Table 2 using a Mitsui Henschel mixer (Mitsui Miike Kakoki Co., Ltd.) at 3000 rpm for 15 minutes to obtain a toner. Obtained. Physical properties of the obtained toner are shown in Table 2 and evaluation results are shown in Table 3.

Claims (8)

A toner having toner particles containing a colorant and a binder resin,
The force between two particles is 1.0 nN or more and 25.0 nN or less when measuring a compact of the toner formed by compressing the toner with a load of 78.5 N.
In the surface potential distribution of the toner particles measured by a scanning probe microscope, the variation coefficient of the surface potential distribution is 50% or less.   The toner according to claim 1, wherein the toner particles have an absolute value of an average surface potential distribution of 1.0 V or more and 15.0 V or less.   The toner according to claim 1, wherein the toner particles have a coefficient of variation of surface potential distribution of 33% or less.   The toner according to claim 1, wherein the toner particles have an interparticle force of 1.0 nN or more and 20.0 nN or less.   The toner according to any one of claims 1 to 4, wherein the toner particles have a surface layer containing an organosilicon polymer.   The toner according to claim 5, wherein the content of the organosilicon polymer in the toner particles is 0.5% by mass or more and 5.0% by mass or less. The toner according to claim 5, wherein the organosilicon polymer is a polymer having a partial structure represented by the following formula (R ^a T3).
^Ra- SiO _3/2 ( ^Ra T3)
(In the formula, R ^a represents a hydrocarbon group having 1 to 6 carbon atoms, an aryl group, or a structure represented by the following formula (i) or formula (ii).

(In the formulas (i) and (ii), * represents a binding site with the Si element in the R ^a T3 structure, and L in the formula (ii) represents an alkylene group or an arylene group.)) In scanning electron microscope observation of the surface of the toner particle, a backscattered electron image of the surface of the toner particle of 1.5 μm square was obtained, and the brightness of 256 gradations from the backscattered electron image on the horizontal axis was based on the number of pixels. When I got the histogram,
The histogram has two maxima P1 and P2 and a minima V between the P1 and P2,
P2 is a maximum value derived from the organosilicon polymer,
The brightness of P1 is 20 or more and 70 or less, the brightness of P2 is 130 or more and 230 or less,
The ratio of the number of pixels of P1 and P2 to the total number of pixels of the backscattered electron image is 0.50% or more,
Based on the brightness Vl of V, the total number of pixels having a brightness of 0 or more (Vl-30) or less is A1, the total number of pixels of brightness (Vl-29) or more (Vl + 29) or less is AV, and the brightness (Vl + 30) or more and 255 or less. The toner according to any one of claims 5 to 7, wherein the following formulas (1) and (2) are satisfied, where A2 is the total number of pixels.
(A1 / AV) ≧ 1.50 (1)
(A2 / AV) ≧ 1.50 (2)

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