JP2001075304A - Toner and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior fluidity without using a fluidizer and to obtain high transfer efficiency by disposing a coating layer formed by fixing granular agglomerates containing at least a silicon compound on the surface of each of toner particles. SOLUTION: A coating layer formed by fixing granular agglomerates containing at least a silicon compound is disposed on the surface of each of toner particles constituting a toner and containing at least a bonding resin and a colorant. When an amount of elemental silicon present on the surfaces of the toner particles is measured by EPMA, the coating layer has a more favorable state preferably in the case of 0.10-10.0 mass%, in particular 0.10-4.0 mass%. The toner has one or more glass transition temperatures at <=60 deg.C, the melting start temperature of the toner is <=100 deg.C and the difference between each of the glass transition temperatures and the melting start temperature is preferably <=38 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic charge image or a toner for forming a toner image in a toner jet type image forming method, and a method for manufacturing the toner. The present invention relates to a toner suitably used for a method of heating and pressing a toner image formed by a toner on a print sheet such as a transfer material, and a method of manufacturing the toner.

[0002]

2. Description of the Related Art In an electrostatic charge developing method, charged toner particles are configured to develop an electrostatic latent image on a drum by electrostatic force according to a potential difference on the drum. At this time, the charging of the toner particles is specifically caused by friction between the toner particles or between the toner particles or between the toner particles and the carrier particles. In order to efficiently and uniformly generate the friction, the toner particles are charged. It is important that the toner maintain fluidity.

On the other hand, as a general method for imparting fluidity to a toner, a fluidizing agent such as inorganic fine particles typified by silica, titanium, and alumina, and organic fine particles of a high molecular compound is used. It is well known how to externally add. In addition, various techniques have been devised for adding the fluidizing agent as described above. For example, a method of attaching the fluidizing agent to the surface of the toner particles by the electrostatic force between the toner particles and the fluidizing agent or the van der Waals force is generally used. As a method for attaching a fluidizing agent to the surface of the toner particles, there is a method using a stirrer or a mixer.

However, in the above-described method, it is not easy to uniformly disperse and attach the fluidizing agent to the surface of the toner particles, and the fluidizing agent that has not adhered to the toner particles forms an aggregate. This makes it difficult to avoid the presence of the so-called "free additive" contained in a free state. In such a case, the fluidity of the developer may be reduced, for example, the amount of triboelectricity may be reduced, and a sufficient image density may not be obtained, or an image having a lot of fog may be formed. Further, as described above, in the conventional case, the fluidizing agent only adheres to the surface of the toner particles by electrostatic force or van der Waals force, so that when a continuous copy is performed, In addition, the release of the fluidizing agent from the surface of the toner particles and the embedding of the fluidizing agent into the toner particles increase, which causes a problem that the image in the early stage of durability cannot be held in the latter half of the continuous copying.

As a method for imparting fluidity to a toner without using a fluidizing agent, for example, JP-A-7-18
As described in Japanese Patent No. 1722, a method of fixing wax fine particles on the surface of toner particles and further providing a polysiloxane layer obtained by polycondensation of aminosilane alkoxide and alkylalkoxysilane on the outside thereof, As described in Japanese Unexamined Patent Publication No. 8-95284, there is known a method of obtaining a toner by polymerizing a monomer system to which an organic silane compound is added. However, the toner obtained by these methods has a problem that the transfer efficiency is reduced because the surface of the toner particles is smooth.

Further, recently, in the field of electrophotography, there has been an increasing movement to obtain higher quality images. And
One of means for achieving high image quality is to sharpen the distribution of the charge amount of the toner used in the developer.
When the charge amount distribution of the toner becomes sharp, the charge amount of each toner particle constituting the toner becomes uniform,
Fogging and scattering of the formed image are reduced, and a toner image that is faithful to the latent image formed on the drum can be reproduced. Generally, since the charge amount of toner particles is proportional to the particle size of toner particles, it is effective to sharpen the particle size distribution of toner in order to sharpen the charge amount distribution of toner. Conceivable. In order to impart sufficient charge to the toner particles, generally, a method of adding a so-called external additive such as an inorganic fine particle typified by silica, titanium, and alumina, or an organic fine particle made of a high molecular compound is employed. ing.

However, these external additives are generally mechanically fixed to the surface of the toner particles by using a stirrer or a mixer. A phenomenon occurs in which the additive is released from the toner particles or is embedded in the toner powder. Then, since the surface state of the toner particles changes due to these phenomena, it is difficult to continuously maintain the charge amount of the toner in the early stage of durability when an image is formed, and the initial sharp There was a problem that it was difficult to maintain the charge amount distribution in durability.

Further, in recent years, as personal computers have become phenomenally widespread, the demand for printers and copiers using an electrophotographic system has been expanding from office use to general users. Along with this, for these electrophotographic printers and copiers, it is desired to reduce the size of the apparatus, save resources in accordance with ecology, reduce costs, and the like. One way to solve these problems is to lower the fixing temperature. As means for achieving this, lowering the molecular weight of the binder resin constituting the toner, lowering the glass transition point (Tg), Attempts have been made to increase the content of wax to be contained. However,
The lowering of the molecular weight of the binder resin and the lowering of the glass transition point lower the melting temperature, but at the same time, deteriorate the storage stability of the toner. And the toners are fused together, resulting in a decrease in fluidity.

In order to solve such a problem, a method using a silane compound has been proposed. For example, JP-A-7-98516 discloses a method of kneading and crosslinking a polyester resin and a metal alkoxide.
No. 9573 proposes a method in which a vinyl resin in which a vinyl monomer and a silane coupling agent having an unsaturated double bond and an alkoxysilyl group are covalently bonded is used as a binder resin. However, in these methods, since the composition of the binder resin is limited or the silane compound is present inside the toner particles, it is necessary to substantially control the conflicting performances of fixing property and storage stability. Was difficult.

As another method, for example, Japanese Patent Laid-Open No.
No. 289,647 discloses a method of coating the surface of a toner particle with a curable silicone resin, Japanese Patent Application Laid-Open No. H8-15894 discloses a toner having a metal alkoxide adhered to the surface of the toner particle, and Japanese Patent Application Laid-Open No. H9-179341 discloses a method. Techniques for covering the surface of toner particles in the form of a continuous thin film using a silane coupling agent have been proposed. In these methods, base particles are formed using a resin having a relatively low Tg, and the surface thereof is coated with a hard material such as a silicone resin or a metal alkoxide to prevent the occurrence of blocking, and at the same time, the fixing temperature is lowered. However, since the surface of these toner particles is not sufficiently covered with the above-mentioned silane compound, or even if the toner particles are covered, the surface of the coating layer is smooth, so that the contact with a fixing member such as a hot roll may be caused. The area was small, the heat absorption efficiency was poor, and a large difference occurred between the Tg of the base particles and the actual melting temperature, making it difficult to achieve sufficient low-temperature fixing.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which has excellent fluidity without using a fluidizing agent and which can obtain high transfer efficiency, and a method for producing the toner. Is to do. An object of the present invention is to provide a toner that does not use a fluidizing agent, so that there is no release of the fluidizing agent even when the development is continuously repeated, and no embedding of the fluidizing agent in the toner particles, and even after durability. An object of the present invention is to provide a toner having an excellent fixing property capable of maintaining a stable image density, and a method for producing the toner. The object of the present invention is
By maintaining the sharpness of the charge distribution of the toner continuously during long-term image output, it is possible to stably obtain high-quality images with high reproducibility of dots with little fogging and scattering. And a method for producing the toner. SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which is excellent in blocking resistance despite being excellently fixed at a low fixing temperature, and a method for producing the toner.

[0012]

The above objects are achieved by the present invention described below. That is, the present invention relates to a toner formed of toner particles having at least a binder resin and a colorant, wherein a coating formed by fixing at least particles of a silicon compound on the surface of the toner particles. A toner particle comprising a layer, and a toner particle comprising a toner particle having a coating layer on the surface, wherein a toner particle preparing step of preparing toner particles having at least a binder resin and a colorant; And a coating layer formed by depositing a polycondensate of a silicon compound on the surface of the toner particles from the outside of the toner particles, so that at least the granular lumps containing the silicon compound adhere to the surface of the toner particles. A method for producing a toner, comprising:
And a method for producing a toner comprising toner particles having a coating layer on the surface, wherein the toner particles comprise at least a binder resin and a colorant, and prepare toner particles containing a silicon compound therein. And subjecting the toner particles to a hydrolysis and polycondensation reaction of a silicon compound on the surface of the toner particles in a liquid selected from the group consisting of water and a mixed solvent of water and an aqueous solvent. A coating layer forming step of forming a coating layer in a state in which granular masses containing at least a silicon compound are fixed to the surface of the toner particles.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. A feature of the toner of the present invention is that a coating layer in a state in which at least granular lumps including a silicon compound are fixed to the surface of toner particles containing at least a binder resin and a colorant constituting the toner is provided. Is to be. In the present invention, the coating layer in a state in which the granular lumps containing at least the silicon compound are fixed to each other, specifically, for example, on the surface of the toner particles by hydrolysis and polycondensation of a silicon compound represented by silane alkoxide. It is a layer that can be formed, and is preferably a layer formed so that fine irregularities on the order of nm are observed on the surface thereof.

As a result of extensive studies by the present inventors, at least the surface of toner particles containing a binder resin and a colorant is
By providing a coating layer in which the above-mentioned granular lumps containing at least a silicon compound are fixed to each other, it is found that a toner having sufficient fluidity can be obtained without using a conventional external additive. The present invention has been reached. Thereby, it turned out that stable charging property can be maintained. Furthermore, since no external additive is used, even when the development is performed continuously, the external additive is not released or the external additive is not embedded in the toner particles, and the durability is excellent. all right.

Hereinafter, the "coating layer in which the granular lumps containing at least the silicon compound are fixed" provided on the surface of the toner particles will be described in detail. The present inventors have studied the surface state of the toner having the above-described excellent action as described above, and have obtained the following findings. First, the cross section of the particles constituting the toner of the present invention was examined with a transmission electron microscope (T
By observing with EM), it was possible to observe a state in which a layered structure composed of granular lumps having a diameter of several tens of nm was formed on the surface of the toner particles. Furthermore,
Electron probe microanalysis using scanning electron microscope (SEM) equipped with an X-ray microanalyzer (elec
As a result of examining the surface composition of the toner particles before and after cleaning the toner with a surfactant by tron probe microanalysis (EPMA), it was found that the reduction rate of the silicon element caused by the cleaning was small, and the granular mass containing the silicon compound was obtained. Is not simply attached to the toner particle surface,
Present on the surface of the toner particles in a state where the granular masses are fixed,
It was confirmed that the coating layer was formed.

Hereinafter, a method for confirming the layer structure of the coating layer formed by fixing the granular lumps containing at least the silicon compound, which is a component of the toner of the present invention, will be described. In the following procedure, a coating layer formed by fixing at least the granular lumps containing the silicon compound was confirmed.

<< Confirmation of Coating Layer Formed by Attachment of Granular Lumps Containing Silicon Compound >> Confirmation of Presence or Absence of Layer Structure by Observation with Transmission Electron Microscope Particles of toner to be measured are embedded in epoxy resin. After hardening with a microtome, an ultra-thin section of the toner particles was created, and this was fixed in a measuring cell for a transmission electron microscope,
This was used as a sample. The above sample was observed at a magnification of 10,000 to 50,000 times with a Hitachi H-7500 type transmission electron microscope, and it was confirmed that a layer structure of a granular mass was present on the toner particle surface.

Confirmation of sticking of granular lumps by the reduction rate of the amount of silicon element on the surface of the toner particles after washing with the surfactant The amount of silicon atoms (% by mass) on the particle surface of the toner by electron probe microanalysis. Measurement) The surface of the toner particles was subjected to an accelerating voltage of 20 kV by using an S-4500 type field emission scanning electron microscope manufactured by Hitachi, Ltd. equipped with an X-ray microanalyzer X-5770W manufactured by Horiba, Ltd. , Sample absorption current value 1.0 ×
Electron probe microscopic analysis was performed under the conditions of 10 ^-10 A and 25,000 times, and the abundance of silicon atoms when the total amount (% by mass) of carbon atoms, oxygen atoms, and silicon atoms was 100% Si ₁ (% by mass) was measured. The measurement was performed for 20 visual fields, and the average value was used as the measured value.

Cleaning of Particle Surface of Toner with Surfactant 0.2 g of the toner was dispersed in 5 ml of a 5% aqueous solution of dodecylbenzenesulfonic acid, and the resulting mixture was subjected to an ultrasonic cleaner for 30 minutes to sufficiently clean the particle surface of the toner. Further, centrifugation and washing were repeated to completely remove dodecylbenzenesulfonic acid from the toner particle surface, and then dried under reduced pressure to isolate the toner.

Measurement of silicon atom abundance (% by mass) on toner particle surface after washing with surfactant surfactant The amount of silicon atom (% by mass) desorbed from toner particle surface by the above operation was measured. In order to carry out the analysis, in the same manner as described above, an electron probe microscopic analysis of the particle surface of the toner after the cleaning with the surfactant was performed, and the abundance S of silicon atoms was determined.
i ₂ (% by mass) was measured.

Analysis of State of Coating Layer Formed by Granular Lumps Containing Silicon Compound Provided on the Surface of Toner Particles From the values of Si ₁ and Si ₂ obtained by the above procedures, the surface activity is calculated by the following equation. The reduction rate of the abundance of silicon element on the surface of the toner particles caused by the washing of the agent was calculated. When the rate of reduction of the abundance ratio of the silicon element on the surface of the toner particles is extremely small, the coating layer formed on the surface of the toner particles by the granular lumps containing the silicon compound adheres in a state where it is difficult to fall off the surface. It can be determined that there is. Accordingly, when the reduction rate of the abundance of the silicon element on the surface of the toner particles obtained by the following formula is 30% or less, the coating layer formed on the surface of the toner particles is formed by removing the silicon compound constituting the layer. It is considered that the granular masses including the silicon compound are in a state of being firmly fixed to each other, and a means for confirming whether or not the granular masses containing the silicon compound are in the state of being firmly fixed to each other is used.

[0022]

(Equation 1)

As described above, in the present invention,
Combine the visual confirmation of the layer structure with the granular mass by transmission electron microscopy observation and the measurement result of the reduction rate of the abundance of silicon element on the particle surface of the toner before and after washing with the surfactant. Coating layer formed by fixation of granular lumps containing silicon compound "
Confirmation means.

As confirmed by the above-mentioned method, in the toner of the present invention, the coating layer on the surface of the toner particles constituting the toner is fixed to the granular mass containing at least the silicon compound. As a result, fine irregularities exist on the surface of the toner particles, thereby realizing high transfer efficiency. In the present invention, as a typical example of the production of a toner, a coating layer is formed on the surface of toner particles by a polycondensate of a silicon compound by a sol-gel method described below. It is in the form of a film, and is a film in which granular masses containing polycondensates of silicon compounds are chemically bonded to each other to form a coating layer covering the entire surface of the toner particles. For this reason, as in the case where a conventional fluidizing agent such as silica is adhered to the surface of the toner particles described above, there is room for generation of unattached free fine particles caused by the addition of the fluidizing agent and free fine particles due to deterioration in durability. There is no. For this reason,
The toner of the present invention has excellent durability.

According to a detailed study of the present inventors, the EPM
When the amount of silicon element present on the particle surface of the toner is measured by A, the amount is preferably 0.10 to 2
0.0 mass%, more preferably 0.1 to 10.0
Mass%, more preferably 0.10 to 4.0 mass%.
It has been found that a coating layer in a more preferable state can be obtained when it is within the range. That is, a case where a coating layer formed by fixing particulate masses containing a silicon compound such that the abundance of silicon atoms on the toner particle surface is 0.10% by mass or more is provided on the surface of the toner particles. Furthermore, it was confirmed that higher fluidity and higher transfer efficiency can be imparted to the toner. Further, when the amount of silicon atoms present on the surface of the toner particles provided with the coating layer formed by fixing the granular lumps containing the silicon compound is 0.10% by mass or more, the granular Since the surface of the toner particles is covered in a sufficient state by the coating layer formed by fixing the lumps, a higher fluidity can be imparted to the toner and a sufficient charge amount can be imparted to the toner. A toner is obtained. On the other hand, when the amount of silicon atoms on the surface of the toner particles is 2
By providing a coating layer that is 0.0% by mass or less,
It was found that the toner exhibited better fixability. This is because, in the case of a coating layer in which the amount of silicon atoms present on the surface of the toner particles satisfies the above conditions, the thermoplasticity of the binder resin constituting the toner particles is sufficiently exhibited. I think that the.

In the present invention, since the toner is formed by providing the above-mentioned specific coating layer on the surface of the toner particles serving as the base, the melting temperature of the binder resin forming the toner is lowered. The fixability can be improved, and even in such a toner, even in a high-temperature environment, fusion to the inside of a developing device or fusion between toners occurs and fluidity is reduced. It is possible to obtain a toner that simultaneously satisfies the function of having excellent storage stability without causing a decrease. As a composition of such a toner having excellent fixing properties, the toner has at least one glass transition point at 60 ° C. or less, a melting start temperature of 100 ° C. or less, and further has a glass transition point and The difference from the melting start temperature is preferably 38 ° C. or less.

In the case of the toner having the above structure, EPMA
When the abundance of the silicon element on the surface of the toner particles of the toner measured by the method described above is in the range of 0.10 to 10.0% by mass, and preferably in the range of 0.1 to 4.0% by mass, a preferable coating layer is formed. Obtainable. By providing a coating layer formed by fixing particulate agglomerates containing a silicon compound such that the abundance of silicon atoms on the surface of the toner is 0.10% by mass or more on the surface of the base toner particles, It is considered that the sol-gel film was able to sufficiently contain the toner particles serving as the base, and exhibited excellent blocking resistance. On the other hand, if the amount of silicon atoms present on the surface of the toner particles provided with the coating layer formed by fixing the granular lumps containing the silicon compound is less than 0.10% by mass, This means that the amount of the sol-gel film on the surface is small, so that the sol-gel film does not sufficiently cover the surface of the toner particles serving as the base, and the blocking resistance of the toner is impaired.

When the coating layer is provided so that the amount of silicon atoms present on the surface of the toner particles is 10.0% by mass or less, good fixability of the parent toner particles can be maintained. That is, when such a coating layer is formed, the thermoplasticity of the binder resin constituting the base toner particles is sufficiently exhibited without being impaired by providing the coating layer. .

Further, since the coating layer formed on the surface of the toner is formed by fixing at least the granular lumps containing the silicon compound, the surface of the toner particles constituting the toner has fine irregularities. However, since the surface area is increased, the contact area between the fixing member such as a heat roll and the toner is increased, and the heat absorption efficiency is improved. As a result, there is less difference between the Tg and the melting start temperature of the base toner particles and that of the toner, as compared with the toner having the conventional coating layer provided for the purpose of blocking resistance. Sufficient low-temperature fixing can be achieved. In addition, a coating layer provided on the surface of the toner particles is typically formed by a method of depositing a polycondensate of a silicon compound on the particle surface by a sol-gel method described below. In the form, the film in the state where the granular mass containing the polycondensate of the silicon compound is chemically bonded is in the form of a coating layer covering the entire surface of the toner particles, and thus has excellent low-temperature fixability with a low glass transition point. The surface of the toner particles using the binder resin as a main component is sufficiently wrapped, and as a result, the toner does not fuse together even in a high temperature environment.

Further, according to the study of the present inventors, in the toner of the present invention, the granular lumps containing the silicon compound provided on the surface of the toner particles containing at least the binder resin and the colorant adhere to each other. In order for the coating layer to be formed by the above-mentioned process to have the above-described excellent action, the coating layer is formed mainly near the surface of the toner particles. It turned out to be necessary. That is, for example, when a polycondensate of a silicon compound, which is a preferred component of the coating layer formed by fixing the granular lumps containing the silicon compound described above, is present even inside the toner particles. It has been found that the toner has a tendency to lose the thermoplasticity of the binder resin constituting the toner particles and to impair the fixability of the obtained toner.

As a result of further detailed examination by the present inventors, EPMA is required as a requirement for a coating layer formed by fixing together granular particles containing a silicon compound formed near the surface of toner particles. When the total amount of carbon atoms, oxygen atoms and silicon atoms in the cross section of the toner particles is 100%, the measured value of silicon atoms (% by mass) is 4.0%. %, It was confirmed that a toner having sufficient fixability could be obtained. That is, the fact that the abundance of silicon atoms in the particle cross section of the toner exceeds 4.0% by mass means that the silicon compound, which is a component of the coating layer formed by fixing the granular lumps containing the silicon compound, to each other. This means that the polycondensate exists even inside the toner particles, and as a result, it is considered that the fixability is impaired.

A method for measuring the abundance (% by mass) of silicon atoms in the cross section of the toner particles specified in the present invention will be described. << Method of Measuring Abundance of Silicon Atoms in Toner Section of Toner >> After embedding and solidifying the toner particles to be measured in an epoxy resin, an ultrathin section of the toner particles is prepared by a microtome to prepare a sample for measurement. This sample is placed on an aluminum sample stand for scanning electron micrographs, and fixed using a conductive carbon adhesive sheet.
For this sample, the amount of silicon atoms was quantified in the same manner as the above-described method for measuring the amount of silicon atoms present on the particle surface of the toner.

In the toner of the present invention, when the amount of silicon atoms present on the particle surface of the toner measured by the above-described method is at least twice as large as the amount of silicon atoms present on the cross section of the toner particles, A favorable effect can be obtained. That is, according to the investigations of the present inventors, when an image is formed using a toner provided with a coating layer formed by fixing particulate lumps containing a silicon compound having such requirements, In addition, it was found that better fixability was obtained. This is because the coating layer having such a configuration is further formed near the surface of the toner particles, so that the thermoplasticity of the binder resin is formed by fixing at least the granular masses containing the silicon compound. It is considered that the coating was not impaired by the formation of the coating layer, so that the fixing property was more excellent.

Further, as a result of a series of studies on the present invention, it has been found that, in the toner of the present invention, more favorable effects can be obtained when the amount of silicon atoms present on the particle surface of the toner is 4.0% by mass or less. I understood. Such a configuration is easily achieved by using a compound having an organic substituent in the silicon compound in the coating layer formed by fixing the granular masses containing at least the silicon compound. It was also found that the durability of the toner could be further improved. This is probably due to the use of those having organic substituents in the silicon compound in the coating layer, which added the flexibility of the organic chains to the formed coating layer, resulting in excellent durability. Believe in things.

That is, when there is an organic substituent in the silicon compound in the coating layer formed by fixing at least the granular lumps containing the silicon compound, the amount of carbon atoms present on the particle surface of the toner increases. In other words, when the total amount of carbon atoms, oxygen atoms and silicon atoms is assumed to be 100%, the amount of silicon atoms is considered to be reduced. As a result of comparing and examining the abundance of atoms and the durability of the toner, the abundance of silicon atoms on the particle surface of the toner was 100% of the total abundance of carbon atoms, oxygen atoms and silicon atoms.
When the content is 4.0% by mass or less, it is found that the durability of the coating layer formed becomes higher, which makes it possible to further improve the durability of the toner of the present invention. .

In the toner of the present invention in which the coating layer in which the granular particles containing at least the silicon compound are fixed on the surface of the toner particles is provided, the unreacted silanol groups (-SiOH) remain on the surface of the toner particles. It was found that it is preferable to treat the surface of the coating layer with a coupling agent in order to maintain a sufficient charge amount under high temperature and high humidity conditions. That is, when the coupling agent is treated on the surface of the coating layer in a state where the particles containing at least the silicon compound are fixed to each other, the coating layer is provided on the surface of the toner particles, so that the particles remain on the surface of the toner particles. Since the hydroxyl groups of the unreacted silanol groups are capped, the effect of moisture in the air can be reduced, and a toner that can maintain sufficient chargeability even under high temperature and high humidity can be obtained. It is possible to further enhance the function of the coating layer on the surface of the toner particles.

In the present invention, the toner has a number average particle diameter in the range of 0.1 μm to 10.0 μm, and
It is preferable to have a sharp particle size distribution of small particle sizes having a coefficient of variation of a number distribution of 0.0% or less in order to form a high quality image. By controlling the size and particle size distribution of the toner in this way, when the toner is used, the charge amount distribution of the toner becomes sharp, and it is possible to obtain an image with little fog and scattering and high dot reproducibility. become. When the number average particle diameter of the toner is smaller than 0.1 μm, it becomes difficult to handle the powder.
If it is larger than 0.0 μm, the particle size of the toner may be too large for the latent image, and it is difficult to faithfully reproduce the dots. Further, if the variation coefficient of the number distribution representing the particle size distribution is wider than 20.0%, the charge amount varies, resulting in an image with a lot of fog and scattering, and the dot reproducibility is lowered. In the present invention, in order to achieve the above object, the number average particle diameter of the toner is more preferably 1.0 μm to 8.0 μm, and still more preferably 3.0 μm.
The variation coefficient of the number distribution of the toner is more preferably 15.0% or less, and further preferably 10.0% or less. The charge amount distribution of the toner having the above-described coating layer provided on the surface of the toner particles having a sharp particle size distribution is maintained even after long-term durability.

The method for measuring the number average particle size and the particle size distribution of the toner used in the present invention will be described below. First, using a Hitachi S-4500 Field Emission Scanning Electron Microscope, take a 5,000-fold photo of the toner, and from the photo, determine the size of each toner particle so that the accumulation of toner particles becomes 300 or more. The diameter was measured, and the number average particle diameter was calculated from these measured values. Further, the coefficient of variation of the number distribution of the toner was determined by the following equation.

(Equation 2)

Further, in addition to the above-mentioned shape characteristics, the toner of the present invention has at least one glass transition point at a temperature of 60 ° C. or less and a melting onset temperature of 100 ° C. Further, the difference between the glass transition point and the melting start temperature is preferably 38 ° C. or less, whereby a fixing temperature lower than the conventional fixing temperature can be realized. The coating layer provided on the particle surface can also satisfy the blocking resistance.

Hereinafter, specific thermal characteristics of the toner will be described. According to the study of the present inventors, when the toner has one or more glass transition points at least at 60 ° C. or less and does not satisfy the requirement that the melting onset temperature is 100 ° C. or less, it will be described later. In the fixing test, it was found that the toner sometimes did not show good fixing property. Further, when the difference between the glass transition point and the melting start temperature is larger than 38 ° C., the low-temperature fixability of the toner particles serving as a base is not maintained, and the toner after the toner particles are coated with the sol-gel film has the fixability. Good fixability is not shown in the test.

As described above, in order to control the melting start temperature and the glass transition point of the toner, the thermal characteristics of the base toner particles (the toner particles before the coating layer is applied) are, for example, 1) The resin composition 2) the molecular weight and molecular weight distribution of the binder resin 3) the content of the wax and the release agent may be controlled. Then, the glass transition point (Tg) of the base toner particles is
At least 60 ° C or lower, more preferably 40 ° C or lower,
It is preferable to control at least one of Tg and the melting start temperature to be 100 ° C. or lower, more preferably 80 ° C. or lower.

In the case where the melting temperature is adjusted by the amount of the release agent contained in the toner, when the amount of the release agent is 80% by mass or more based on the weight of the toner including the coating layer, the transfer is performed. An image fixed on paper, film, or the like may be peeled off, which is presumed to be practically impossible. Considering the releasability from the fixing roller and the like, it can be said that a form containing a release agent is more preferable. Therefore, in the toner of the present invention, the content of the release agent is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass as a whole.

The release agent that can be used in the present invention is preferably a solid wax that is solid at room temperature. Specifically, a solid wax that is solid at room temperature is preferable. Specific examples include paraffin wax, polyolefin wax, Fischer-Tropsch wax, amide wax, higher fatty acid, ester wax, and derivatives such as graft compounds and block compounds. An ester wax having at least one long-chain ester moiety having 10 or more carbon atoms represented by the following general structural formula is particularly preferred because it has an effect on high-temperature offset resistance without inhibiting transparency of OHP. The structural formulas of representative compounds of preferred specific ester waxes that can be used in the present invention are shown below as general structural formulas (1) to (5).

[0044]

Embedded image (In the formula (1), a and b each represent an integer of 0 to 4, and a + b
Is 4, R ₁ and R ₂ represent an organic group having 1 to 40 carbon atoms, and a group having a carbon number difference of 10 or more between R ₁ and R _2, and n and m represent 0 to 0. Indicates an integer of 15, and n and m are never 0 at the same time. )

[0045]

Embedded image (In the formula (2), a and b represent an integer of 0 to 4, and a + b
Is 4, R ₁ represents an organic group having 1 to 40 carbon atoms,
n and m each represent an integer of 0 to 15, and n and m do not become 0 at the same time. )

[0046]

Embedded image (In the formula (3), a and b each represent an integer of 0 to 3, and a + b
Is 3 or less, R ₁ represents an organic group having 1 to 40 carbon atoms, n and m each represent an integer of 0 to 15, and n and m are not simultaneously 0. )

[0047]

Embedded image (In the formula (4), R ₁ and R ₂ each represent a hydrocarbon group having 1 to 40 carbon atoms, and R ₁ and R ₂ may have the same or different carbon atoms.)

[0048]

Embedded image (In the formula (5), R ₁ and R ₂ each represent a hydrocarbon group having 1 to 40 carbon atoms, n is an integer of 2 to 20, and R ₁ and R ₂ are the same or different. The carbon number may be used.)

The method of measuring the glass transition point and the melting start point used in the present invention will be described below. (Measurement of Glass Transition Point) The glass transition point Tg of the resin was measured according to ASTM D3418-82 using a DSC-7 (manufactured by PerkinElmer).

(Measurement of Melting Start Temperature) The measurement of the melting start point in the present invention was carried out using a flow tester CFT-500 type (manufactured by Shimadzu Corporation). About 1.0 to 1.5 g of a sample to be measured is weighed, and this is
1 with a load of 0.665 kPa (100 kgf / cm ² )
Pressurize for a minute to make a pressurized sample. This pressurized sample is subjected to the following conditions under normal temperature and normal humidity (temperature about 20 to 30 ° C,
Perform a flow tester measurement at a humidity of 30 to 70% RH)
Obtain a humidity-apparent viscosity curve. From the obtained smooth curve, the temperature at which the viscosity began to decrease was read as the melting start temperature.

• RATE TEMP: 6.0 (° C./1 minute) • SET TEMP: 70.0 (° C.) • MAX TEMP: 200.0 (° C.) • INTERVAL: 3.0 (° C.) • PREHEAT: 300. 0 (second) • LOAD: 20.0 (kgf) • DIE (DIA): 1.0 (mm) • DIE (LENG): 1.0 (mm) • PLUNGER: 1.0 (cm ² )

Next, a description will be given of a method of producing a toner which can obtain the toner of the present invention having a coating layer formed by fixing granular lumps containing at least a silicon compound on the surface of toner particles. I do.

In the method for producing a toner according to the present invention, toner particles comprising at least a binder resin and a colorant are prepared, and granular masses containing at least a silicon compound are fixed to the surface of the toner particles by a method described later. To form a coating layer. As the toner particles, any conventionally known toner particles containing at least a binder resin and a colorant, and if necessary, various additives may be used. That is, the toner particles used in the present invention may be a so-called pulverized toner obtained by kneading a toner composition comprising a binder resin and other optional components, cooling the kneaded material, and pulverizing the kneaded material. Alternatively, it may be a so-called polymerization toner obtained by polymerizing a polymerizable monomer to be a binder resin. However, in the toner of the present invention, if the shape of the toner particles is irregular, friction between the toner particles causes the coating layer formed on the surface to be easily deteriorated. It is more preferable to use spherical toner particles. Incidentally, the spherical toner particles can be obtained by spheroidizing the toner particles produced by the pulverization method, or
It can be easily obtained by producing toner particles by a polymerization method.

As a typical example of the production of the coating layer formed by fixing the granular lumps containing at least the silicon compound of the present invention, application of a method generally called a sol-gel method may be mentioned. it can. Hereinafter, a production example by the sol-gel method will be described. The sol-gel method is generally known as a technique for producing a planar metal compound polycondensation film or a solid metal compound polycondensate.
It is generally called a sol-gel film.

The sol-gel film is specifically formed by hydrolytic polycondensation of a silicon compound typified by silane alkoxide, and its surface has fine irregularities on the order of nm. The present inventors have conducted intensive studies, and as a result, by providing this sol-gel film on the surface of the toner particles, a sufficient charge amount can be imparted without using an external additive as in the conventional toner. ,and,
It has been found that a toner is obtained in which the performance of the toner hardly deteriorates due to durability.

Further, the present inventors have conducted intensive studies, and as a result,
By providing a sol-gel film having the above-described properties on the surface of the toner particles, the toner containing the binder resin having a low Tg can be prevented from blocking while maintaining its low-temperature fixability. all right.

As a first method for forming a coating layer formed by fixing at least particles containing a silicon compound on the surface of toner particles, a toner containing at least a binder resin and a colorant is used. From outside the particle,
There is a method in which a polycondensate of a silicon compound is deposited on the surface of the toner particles to form the coating layer on the surface of the toner particles. Specifically, a method of dispersing the base toner particles in water or an aqueous medium in which silane alkoxide is dissolved, and then dropping this dispersion solution into water or an aqueous medium to which an alkali has been added. is there. According to this method, the silane alkoxide dissolved in the dispersion solution containing the toner particles undergoes hydrolysis and polycondensation in the presence of an alkali, gradually insolubilizes, and further becomes hydrophobic. The interaction results in deposition on the surface of the toner particles. As a result, a coating layer is formed on the surfaces of the toner particles by fixing the granular lumps containing at least the silicon compound. Further, when the toner particles obtained by the dispersion polymerization described above are used, the reaction system after the completion of the polymerization of the parent toner particles may be cooled to room temperature, and then the silane compound may be dissolved therein and used as a toner dispersion. it can.

As the aqueous medium used above, for example, alcohols such as methanol, ethanol and isopropanol are used. When the organic nature of these solvents increases, the solubility of the polycondensate of silane alkoxide increases. This makes it difficult for polycondensates of silane alkoxide to deposit on the surface of the toner particles. Therefore, it is preferable to use methanol or ethanol as the aqueous medium.

As a second method of forming a coating layer formed by fixing at least particles containing a silicon compound on the surface of toner particles, at least a binder resin and a colorant are contained. And, by dispersing the toner particles in which the silicon compound is contained, in water, or a mixed solvent of an aqueous solvent and water, hydrolysis and polycondensation of the silicon compound are performed on the surface of the toner particles, There is a method of forming the coating layer.

In the above method, the toner particles
When dispersed in water or a mixed solvent of an aqueous solvent and water, the silicon compound contained in the toner particles comes into contact with water on the surface of the toner particles and undergoes hydrolysis. That is, the sol-gel reaction proceeds only near the surface of the toner particles. Further, after the reaction is completed, by washing with a solvent such as alcohol, unreacted silicon compounds remaining inside the toner particles can be removed. As a result, a polycondensate of the silicon compound is selectively present on the surface of the toner particles, and the coating layer is formed by fixing at least the granular lumps containing the silicon compound,
In addition, it is possible to form a coating layer in which the amount of silicon atoms present on the surface of the toner particles is larger than the amount present inside the toner particles.

Here, the aqueous solvent refers to a solvent that can be dissolved in water, and the aqueous solvent suitable for dispersing the toner particles, which is suitable for the above method, is methanol,
Examples include alcohols such as ethanol and propanol, and mixed solvents thereof.

As a method of preliminarily incorporating the silicon compound in the toner particles, the silicon compound may be mixed at the time of the production of the toner particles, or the mother particles may be prepared by a conventional method and then added to the obtained particles. May be introduced. In this case, as a method of introducing the silicon compound into the toner particles after preparing the toner particles serving as the base, the silicon compound is swollen into the toner particles serving as the base in water or a mixed medium of water and an aqueous medium. Is effective. Specifically, the following methods are mentioned.

Specifically, for example, there is a method in which the toner particles serving as the base and the silicon compound are dispersed in a liquid medium in which the silicon compound does not dissolve, typically in water. In this way, the silicon compound slightly dissolved in the liquid medium,
The silicon compound is absorbed into the toner particles due to physical contact between the dispersed silicon compound and the toner particles, or the silicon compound is absorbed into the toner particles by diffusing in the liquid medium, and the silicon compound is incorporated into the toner particles. Can be introduced. In this case, it is preferable to use a surfactant in order to stably disperse the silicon compound in the liquid medium.
As the surfactant, a conventionally known general agent can be used.

At this time, when a dispersion of the toner particles and a dispersion of the silicon compound are separately prepared and both are mixed,
It is not preferable to add the silicon compound dispersion to the toner particle dispersion because the toner particles tend to coalesce, resulting in a toner having a broader particle size distribution than the toner particles before the reaction. As a result, the obtained toner tends to have a problem that the distribution of the triboelectric charge amount becomes broad and the image is scattered. Therefore, in a case where a dispersion of toner particles and a dispersion of silicon compound are separately prepared and mixed, a method of adding the dispersion of toner particles to the dispersion of silicon compound is more preferable.

In order to maintain the particle size distribution of the toner particles before forming the coating layer after forming the coating layer on the surface of the toner particles to obtain the toner of the present invention, the silicon compound is added to a liquid medium such as water. When dispersing, it is more preferable to disperse the silicon compound for the individual toner particles into as small droplets as possible. Further, as the method, it is preferable to use a method of mechanically stirring with a high-speed stirrer or the like, or a method of finely dispersing with an ultrasonic disperser or the like.

As described above, when the silicon compound is swelled and incorporated in the toner particles, the silicon compound and another poorly water-soluble solvent are used in combination for the auxiliary purpose such as increasing the swelling speed. A silicon compound can be swelled therein. As the poorly water-soluble solvent used at this time, any solvent may be used as long as it is a solvent having a higher hydrophilicity than the silicon compound to be used and a solvent which is hardly soluble in water. Specific examples include isopentyl acetate, isobutyl acetate, methyl acetate, ethyl acetate and the like. When using these poorly water-soluble solvents, at any stage after the start of the polycondensation reaction of the silicon compound, by evaporating the poorly water-soluble solvent or by charging the toner particles into a hydrophobic medium, It is necessary to dissolve the poorly water-soluble solvent in the hydrophobic medium and remove it from the toner particles.
By performing the above operation, the unreacted silicon compound remaining in the toner particles can also be removed.

Further, as another method of swelling the silicon compound inside the toner particles serving as a base, the toner particles are dispersed in a liquid medium in which the silicon compound is dissolved, typically, alcohol, and the silicon compound is dispersed. There is a method of introducing a silicon compound into a toner by lowering the solubility. Examples of the method of lowering the solubility of the silicon compound include a method of lowering the temperature and gradually adding a liquid medium which is soluble in the liquid medium in which the silicon compound is soluble and which does not dissolve the silicon compound. As the latter method, specifically, for example, after dissolving a silicon compound in a low molecular weight alcohol such as methanol and dispersing the toner particles serving as a base, water is gradually added to lower the solubility of the silicon compound. And a method in which the silicon compound is swollen into toner particles and contained therein.

As described above, when the method of dissolving the silicon compound and introducing the silicon compound into the inside of the toner particles is used, if the solubility of the silane alcohol after hydrolysis is high, the Since the silane alcohol dissolves into the medium from the surface and the dissolved silane alcohols may form particles alone, select a medium in which the silane alcohol obtained by hydrolyzing the silicon compound is hardly soluble. There is a need to.

The stirring speed when the polycondensation reaction of the silicon compound proceeds on the surface of the toner particles serving as the base where the silicon compound is in a swollen state depends on the particle concentration in the system, the size of the system, the amount of swelling of the silicon compound, and the like. Although it depends on the particles, it is easy for the particles to coalesce if they are too slow or too fast,
Because it may cause the particle size distribution of the obtained toner to be disturbed,
The speed needs to be adjusted appropriately. In the above case, a general surfactant, a polymer dispersant, a solid dispersant, or the like may be used in order to stably disperse the base toner particles in the poorly water-soluble medium.

In the toner of the present invention, the coating layer formed on the surface of the toner particles and formed by fixing the granular lumps containing at least the silicon compound is specifically formed of silane by the method described above. It is a coating layer composed of a polycondensate of a silicon compound obtained by hydrolyzing a silicon compound such as alkoxide and then subjecting the compound to polycondensation. The above reaction basically proceeds at room temperature.

To obtain a film-like polycondensate as described above,
It is necessary to use at least one silicon compound having at least two hydrolysis and polycondensation groups in one molecule. However,
Monofunctional compounds can be used in combination. Therefore, in the present invention, the following silicon compounds can be used when forming a coating layer formed by fixing at least the granular masses containing the silicon compound.

Examples of the bifunctional or higher functional silane alkoxide include, for example, tetramethoxysilane, methyltriethoxysilane, hexyltriethoxysilane, triethoxychlorosilane, di-t-butoxydiacetoxysilane, hydroxymethyltriethoxysilane, tetraethoxysilane. Silane, tetra-n-propoxysilane, tetrakis (2-methacryloxyethoxysilane) silane, allyltriethoxysilane, allyltrimethoxysilane,
-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) methane, bis (triethoxysilyl) 1,7-octadiene, 2,2-
(Chloromethyl) allyltrimethoxysilane, ((chloromethyl) phenylethyl) trimethoxysilane, 1,
3-divinyltetraethoxydisiloxane, 2- (3,
4-epoxycyclohexyl) ethortrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3-mercapto Propyltriethoxysilane, methacrylamidopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3- (methacryloxypropyl) trimethoxysilane, 1,7-octadienyltriethoxysilane, 7- Octenyltrimethoxysilane,
Examples thereof include tetrakis (ethoxyethoxy) silane, tetrakis (2-methacryloxyethoxy) silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, and vinyltriphenoxysilane.

The monofunctional silane alkoxide which can be used in combination with the above-mentioned bifunctional or higher silane alkoxide is, for example, (3-acryloxypropyl)
Dimethylmethoxysilane, o-Acryloxy (polyethyleneoxy) trimethylsilane, Acryloxytrimethylsilane, 1,3-Bis (methacryloxy) -2-trimethylsiloxypropane, 3-Chloro-2-trimethylsiloxypropene, (Cyclohexenyloxy) trimethyl Silane, methacryloxyethoxytrimethylsilane,
(Methacryloxymethyl) dimethylethoxysilane.

Further, as a sol-gel reactive compound other than silane alkoxide, for example, aminosilane such as 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilazane may be used. it can. These sol-gel reactive compounds can be used alone or
More than one type may be used in combination. In general, it is known that, in a sol-gel reaction, the bonding state of a sol-gel film generated varies depending on the acidity of a reaction medium. Specifically, when the medium is acidic, H ⁺ is electrophilically added to oxygen of the alkoxy group (（OR group) and is eliminated as an alcohol. The water then attacks nucleophilically and is replaced by a hydroxy group. At this time, when the content of water in the medium is low, the substitution reaction of the hydroxy group is particularly slow, so that a polycondensation reaction occurs before all of the alkoxy groups attached to the silane are hydrolyzed, so that the one-dimensional reaction can be performed relatively easily. Linear polymers and two-dimensional polymers are easily generated.

On the other hand, when the medium is alkaline, OH ⁻
The alkoxy group is easily changed to silane alcohol by the nucleophilic substitution reaction of In particular, when a silicon compound having three or more alkoxy groups in the same silane is used,
Polycondensation occurs three-dimensionally, and a polymer having many three-dimensional cross-links, that is, a sol-gel film having high strength is generated. Also, the reaction is completed in a short time. Therefore, in order to form a sol-gel film on the surface of the toner particles serving as a base, it is preferable to carry out the sol-gel reaction under alkalinity, and specifically, it is preferable to carry out the reaction under alkaline conditions having a pH of 9 or more. Thereby, a sol-gel film having higher strength and excellent durability can be formed. Further, the above-mentioned sol-gel reaction basically proceeds even at room temperature, but since the reaction is accelerated by heating, heat may be applied to the reaction system as needed.

Next, a method of further treating the above-mentioned coating layer in which the granular lumps containing at least the silicon compound are fixed to each other with a coupling agent will be described. Coupling agents generally include hydrophobic, ionic, and reactive sites such as metal alkoxides and metal chlorides that bind to functional groups such as hydroxyl groups, carboxyl groups, and epoxy groups exposed on the material surface. It can be described as a molecule formed by binding functional sites such as an alkyl group and an ionic group that give the same. In the present invention, utilizing the property that this coupling agent reacts with the hydroxyl group on the material surface, when forming a coating layer surface in a state in which the granular mass containing at least the silicon compound is fixed to the toner particle surface, By reacting with the remaining silanol groups and capping the hydroxyl groups on the surface of the toner particles, it is possible to maintain the chargeability of the toner in a good state even under high temperature and high humidity. Therefore, the ideal coupling agent used in the present invention is preferably a compound that easily reacts with a silanol group and does not itself leave an unreacted metal alcohol group. Therefore, compounds generally referred to as terminal blocking agents and capping agents, compounds referred to as silylating agents, and the like also have a function applicable to this purpose. Therefore, in the present invention, these compounds are also broadly defined as coupling agents.

Next, a method of treating a coating layer formed on the surface of toner particles with a coupling agent in the present invention will be described. The method can be performed by a general coupling, capping, or silylation processing method. For example, a coupling agent is dropped into an acidic alcohol solution whose pH is adjusted to 4.5 to 5.5, and then a toner coated with a silane compound is added. After stirring for about 5 minutes, filtration and washing are performed. repetition,
Drying and isolating the toner particles, or dissolving the coupling agent in alcohol, stirring the powder in a strong mixer such as twin coat, and spraying the alcohol solution of the above coupling agent And then, stirring and drying. In the case of preparing an acidic alcohol solution in the former method, when an alkali is used for a reaction when forming a coating layer containing a silicon compound on the surface of the toner particles, the same system is used after removing or neutralizing the alkali. The acid may be adjusted to acidic by adding an acid therein, or the coupling treatment may be performed in an acidic solution which is isolated from an alkaline solution and newly prepared.

Further, in the method for producing a toner according to the present invention, a coupling agent is mixed at the time of forming a coating layer in which at least the particulate mass containing a silicon compound is fixed, and the coupling is performed simultaneously with the formation of the coating layer. Processing can also be performed. In this case, a combination in which the reactivity of the silica monomer for forming the coating layer is higher than the reactivity of the coupling agent is selected. First, the reaction between the silica monomers proceeds, and the coating layer is formed on the surface of the toner particles. It is preferable that the coupling agent be formed, and then the unreacted silanol on the surface of the coating layer react with the coupling agent to perform the coupling treatment on the surface of the coating layer.

Examples of the coupling agent that can be used in the present invention include the following.
Examples of the silica-based coupling agent include the following. First, as a bifunctional or more functional silica-based coupling agent, for example, tetramethoxysilane, methyltriethoxysilane, hexyltriethoxysilane, triethoxychlorosilane, di-t-butoxydiacetoxysilane, hydroxymethyltriethoxysilane, tetramethylsilane Ethoxysilane, tetra-n-propoxysilane, tetrakis (2-methacryloxyethoxysilane) silane, allyltriethoxysilane, allyltrimethoxysilane,
-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) methane, bis (triethoxysilyl) 1,7-octadiene, 2,2-
(Chloromethyl) allyltrimethoxysilane, ((chloromethyl) phenylethyl) trimethoxysilane, 1,
3-divinyltetraethoxydisiloxane, 2- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3-mercapto Propyltriethoxysilane, methacrylamidopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 1,7-octadienyltriethoxysilane, 7-octenyltrimethoxysilane, tetrakis (ethoxyethoxy) Silane, tetrakis (2
-Methacryloxyethoxy) silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyltriphenoxysilane, methacryloxypropylmethyldimethoxysilane and the like.

Examples of the monofunctional silica coupling agent include (3-acryloxypropyl) dimethylmethoxysilane, o-acryloxy (polyethyleneoxy) trimethylsilane, acryloxytrimethylsilane, and 1,3-bis (methacryloxy). -2-trimethylsiloxypropane, 3-chloro-2-trimethylsiloxypropene, (cyclohexenyloxy) trimethylsilane, methacryloxyethoxytrimethylsilane, (methacryloxymethyl) dimethylethoxysilane and the like.

Further, allyloxytrimethylsilane, trimethylchlorosilane, hexamethyldisilazane, dimethylaminotrimethylsilane, bis (trimethylsilyl)
So-called silylating agents such as acetamide, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, and trimethylsilylimidazole can also be used as the coupling agent in the present invention.

Further, as the titanium coupling agent,
For example, O-allyloxy (polyethylene oxide) triisopropoxytitanate, titanium allyl acetoacetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium n-butoxide, titanium chloride triisopropoxide,
Titanium chloride triisopropoxide, titanium di-n
-Butoxide (bis-2,4-pentanedionate), titanium chloride diethoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis (tetramethylheptanedionate) , Titanium diisopropoxide bis (ethyl acetoacetate), titanium ethoxide,
Titanium 2-ethylhexoxide, titanium isobutoxide, titanium isopropoxide, titanium lactate,
Titanium methacrylate isopropoxide, titanium methacryloxyethyl acetoacetate triisopropoxide, (2-methacryloxyethoxy) triisopropoxy titanate, titanium methoxide, titanium methoxypropoxide, titanium methylphenoxide, titanium n-nonyl oxide, Titanium oxide bis (pentanedionate), titanium n-propoxide, titanium stearyl oxide, titanium tetrakis (bis 2,2
-(Allyloxymethyl) butoxide), titanium triisostearolylisopropoxide, titanium methacrylate methoxyethoxide, tetrakis (trimethylsiloxy) titanium, titanium tris (dodecylbenzenesulfonate) isopropoxide, and titanocene diphenoxide. Can be

Examples of the aluminum-based coupling agent include aluminum (III) n-butoxide, aluminum (III) s-butoxide, aluminum (III) s
-Butoxide bis (ethyl acetoacetate), aluminum (III) t-butoxide, aluminum (II
I) di-s-butoxide ethyl acetoacetate, aluminum (III) diisopropoxide ethyl acetoacetate, aluminum (III) ethoxide, aluminum (III) ethoxyethoxy ethoxide, aluminum hexafluoropentanedionate, aluminum (III) ) 3-Hydroxy-2-methyl-4-pyronate, aluminum (III) isopropoxide, aluminum-9-octadecenylacetoacetate diisopropoxide, aluminum (III) 2,4-pentanedionate, aluminum phenoxy Side, aluminum (III) 2,2,6,6-tetramethyl-3,5-
Heptane dionate is exemplified.

These may be used alone or in combination of two or more. The charge amount of the toner can be appropriately adjusted by appropriately combining them or by the amount of processing used. There is no particular limitation on the amount of the coupling agent to be processed. However, if the amount is too large, the coupling agents may bond with each other to form a coating film, which may impair the fixability.

Next, the method of the present invention for producing toner particles serving as a base for forming a coating layer formed by fixing the granular masses containing at least the silicon compound together will be described.

Examples of the polymerizable monomer which can be used when producing the parent toner particles by the polymerization method include styrene, o-methylstyrene, m-methylstyrene, p-methoxystyrene and p-ethyl. Styrene monomers such as styrene and pt-butylstyrene, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, isobutyl acrylate, octyl acrylate, dodecyl acrylate 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, methacrylic acid Isobutyl, n-octyl methacrylate, Dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, diaminomethyl methacrylate, dimethylaminoethyl methacrylate, benzyl methacrylate, crotonic acid, isocrotonic acid, acid phosphoxyethyl methacrylate, acid phosphooxy Acrylic monomers such as propyl methacrylate, acroyl morpholine, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl ether, isobutyl Ether, β-chloroethyl vinyl ether, phenyl vinyl ether,
p-methylphenyl ether, p-chlorophenyl ether, p-bromophenyl ether, p-nitrophenyl vinyl ether, p-methoxyphenyl vinyl ether, vinyl ether monomers such as butadiene, itaconic acid, maleic acid, fumaric acid, itaconic acid Monobutyl, dibasic acid monomers such as monobutyl maleate, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine,
Heterocyclic monomers such as N-vinylimidazole can be exemplified. These monomers may be used alone or in combination of two or more, and a suitable polymer composition can be selected by arbitrarily combining them so as to obtain preferable characteristics.

Further, as a polymerization solvent (a solvent in which the polymerizable monomer is dissolved but the polymer is not dissolved) which can be used when preparing the parent toner particles by the dispersion polymerization method, the polymerization solvent is obtained by polymerization. A product (polymer) that precipitates as the polymerization proceeds can be used. Specifically, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tertiary butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tertiary pentyl alcohol, 1-
Hexanol, 2-methyl 1-pentanol, 4-methyl-2-pentanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2
Linear or branched aliphatic alcohols such as -octanol and 2-ethyl 1-hexanol, butane, 2-methylbutane, n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane, 2,3 -Dimethylbutane, heptane, n-octane, isooctane,
In addition to aliphatic hydrocarbons such as 2,2,3-trimethylpentane, decane, nonane, cyclopentane, methylcyclopentane, methylcyclohexane, ethylcyclohexane, p-menthane, and bicyclohexyl, aromatic hydrocarbons and halogenated carbons Examples include hydrogens, ethers, fatty acids, esters, sulfur-containing compounds, and mixtures thereof.

Further, as the polymer dispersant usable in the dispersion polymerization, specifically, for example, polystyrene,
Polyhydroxystyrene, polyhydroxystyrene-acrylate copolymer, hydroxylstyrene-vinyl ether or vinyl ester copolymer, polymethyl methacrylate, phenol novolak resin, cresol novolak resin, styrene-acryl copolymer, vinyl ether copolymer Specifically, for example, polymethyl vinyl ether, polyethyl vinyl ether,
Polybutyl vinyl ether, polyisobutyl vinyl ether, polyvinyl alcohol, polyvinyl pyrrolidone,
Polyvinyl acetate, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, vinyl chloride, polyvinyl acetal, cellulose, cellulose acetate, cellulose nitrate, alkylated cellulose, hydroxyalkylated cellulose, specifically, hydroxymethyl cellulose, Hydroxypropyl cellulose, a saturated alkyl polyester resin, an aromatic polyester resin, a polyamide resin, a polyacetal, a polycarbonate resin, or a mixture thereof, or can be formed using an arbitrary ratio of the monomers forming the polymer compound described above. Copolymers can be mentioned.

The toner of the present invention can have a melt viscosity characteristic such as offset prevention, if necessary, by containing a high molecular weight component or a gel component as a component of the toner. The introduction of such a component is achieved by using a crosslinking agent having two or more polymerizable double bonds per molecule. As such a crosslinking agent, specifically, for example, divinylbenzene,
Aromatic divinyl compounds such as divinylnaphthalene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,
3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate,
1,6-hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol tetramethacrylate, glycerol acroxydimethacrylate, N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone Can be mentioned.

These can be used alone or in combination of two or more. In addition, these crosslinking agents can be mixed in advance with the polymerizable monomer, or can be appropriately added during the polymerization as needed. The concentration of these crosslinking agents used in the present invention can be appropriately adjusted in consideration of the molecular weight, molecular weight distribution, and the like of the polymer to be produced. It is preferable that the content be in the range of 01 to 5% by mass.

Examples of the binder resin that can be used in the case of producing toner particles by a pulverization method include a styrene-substituted homopolymer such as polystyrene, poly-p-chlorostyrene, and polyvinyl toluene; p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylate ester copolymer, styrene-methacrylic acid copolymer, styrene-α-chloromethyl methacrylate copolymer Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer , Styrene-acrylonitrile-indene copolymer Such styrene copolymers, polyvinyl chloride, phenolic resin, natural modified phenolic resin,
Naturally modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, cumarone indene resin, petroleum resin And the like. Crosslinked styrenic copolymers and crosslinked polyester resins are also preferred binder resins. In the toner of the present invention, a gel component may be contained in the binder resin in order to prevent offset during melting.

As the colorant constituting the toner particles serving as the base, any pigment or dye can be used, and both can be used in combination. As the black colorant to be used, for example, carbon black, a magnetic substance, and a black color tone using a yellow / magenta / cyan colorant shown below are used. As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used. In particular,
C. I. Pigment Yellow 12, 13, 14, 15,
17, 62, 74, 83, 93, 94, 95, 97, 1
09, 110, 111, 120, 127, 128, 12
9, 147, 168, 174, 176, 180, 18
1, 191 are preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, thioindigo compounds and perylene compounds. Specifically, C.I. I. Pigment Red 2, 3,
5, 6, 7, 23, 48: 2, 48: 3, 48: 4,5
7: 1, 81: 1, 144, 146, 166, 169,
177, 184, 185, 202, 206, 220, 2
21, 254 are particularly preferred.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I.
Pigment Blue 1, 7, 15, 15: 1, 15: 2,
15: 3, 15: 4, 60, 62, 66 can be particularly preferably used.

These colorants can be used alone or as a mixture, and can also be used in the form of a solid solution. The amount of the colorant added is preferably 40 to 150 parts by mass per 100 parts by mass of the binder resin when a magnetic material is used, and 100 parts by mass of the binder resin when another colorant is used. It is preferable to add 5 to 20 parts by mass per unit.

Further, the toner of the present invention can be made a magnetic toner by containing a magnetic substance. In this case, the magnetic material can also serve as a colorant. The magnetic material that can be used in the toner of the present invention includes iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; or aluminum, cobalt, copper, lead, magnesium, tin, and zinc of these metals. , Antimony, beryllium, bismuth, cadmium, calcium,
Examples include alloys of metals such as manganese, selenium, titanium, tungsten, and vanadium and mixtures thereof.

The magnetic material used in the toner of the present invention is more preferably a surface-modified magnetic material. Examples of the surface modifier that can be used at this time include a silane coupling agent and a titanium coupling agent. These magnetic materials have an average particle size of 1
μm or less, preferably 0.1 μm to 0.5 μm. The magnetic characteristics when 7.96 × 10 ² kA / m (10 k sled) is applied are as follows. The coercive force (H _c ) is 1.59 ×
10 ^{3 to} 2.39 × 10 ⁴ A / m (20 to 300 Oe), and saturation magnetization (σ _s ) of 50 to 200 A · m
² / kg (50 to 200 emu / g), residual magnetization (σ
_r ) is 2 to 20 A · m ² / kg (2 to 20 emu /
It is preferable to use a magnetic material that is g).

When a magnetic substance is used, the amount of the coloring agent is 40 to 150 per 100 parts by mass of the binder resin.
It is preferable to add in the range of parts by mass, and when other coloring agent is used, 5 to 100 parts by mass of the binder resin is used.
It is preferable to add in the range of 20 parts by mass.

The toner of the present invention can be made a magnetic toner by containing a magnetic powder. In this case, the following magnetic powder can be used. As the magnetic powder that can be used at this time, a substance that is magnetized in a magnetic field is used, for example, fine particles of a ferromagnetic metal such as iron, cobalt, and nickel, or a magnetic oxide such as magnetite and ferrite. Fine particles of the product. These can also serve as a coloring agent.

Further, a charge control agent may be added to the toner of the present invention as needed. In this case, any known charge control agent can be used. However, it is preferable to use a charge control agent that can charge the toner quickly and stably maintain a constant charge amount. Specifically, examples of the negative charge control agent include metal compounds such as salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, and dicarboxylic acid;
Polymer type compounds having sulfonic acid and carboxylic acid in the side chain,
It is preferable to use a boron compound, a urea compound, a silicon compound, calixarene and the like. As the positive charge control agent, for example, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in a side chain, a guanidine compound, an imidazole compound, or the like is preferably used. These charge control agents are preferably added in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

Further, in the toner of the present invention, in order to improve the releasability when used in combination with a hot roll fixing device or the like, toner particles having a low-temperature fluidizing component such as a plasticizer or wax as a base are used. It can also be introduced inside. Examples of the wax that can be used at this time include, for example, paraffin, polyolefin wax and modified products thereof, for example, oxides and grafted products, higher fatty acids and metal salts thereof, higher aliphatic alcohols, higher aliphatic esters, And aliphatic amide wax. In the toner of the present invention, among these waxes, the softening point measured by the ring and ball method (JIS K2531) is as follows:
It is preferable to use one in the range of 30 to 130 ° C. When these waxes are introduced into the toner particles serving as the base, it is preferable to add them in the form of fine powder.

Further, in the toner of the present invention, general inorganic fine particles such as silica, titanium and alumina and organic fine particles are added to the external additive in order to adjust the charge amount applied to the toner particles to an appropriate value. May be used as an auxiliary.

The particle size of the toner of the present invention obtained as described above is not particularly limited, but in order to have high fluidity, the number average particle size must be 0.1 μm It has a small particle size of about 10.0 μm.
It is preferable that the coefficient of variation of the number distribution has a sharp particle size distribution of 20.0% or less. In order to achieve such a particle size and particle size distribution, it is sometimes necessary to use a so-called classification operation in addition to the above-described toner production process. Therefore, in the present invention, it is more preferable to use the above-described dispersion polymerization method when producing the toner particles serving as the base. The dispersion polymerization method generally means that the monomer is dissolved in a polymerization solvent in which the polymerizable monomer dissolves but the polymer does not dissolve in the presence of a particle stabilizer represented by a polymer dispersant. This is a method for producing particles by polymerizing a body, and is a method for producing a toner known as a method for obtaining particles having a uniform particle size distribution. Further, according to this dispersion polymerization method, small particles having a particle diameter of about 1 μm to 5 μm, which is more suitable as a toner, can be produced as compared with other polymerization methods. Therefore, in the present invention, it is more preferable to produce toner particles serving as a base by this dispersion polymerization.

The toner of the present invention having the above configuration can be used as a one-component developer, or can be mixed with a carrier and used as a two-component developer. When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is preferably in the range of 2 to 15% by mass as the toner concentration in the developer. . That is, if the toner concentration is less than 2% by mass, the image density tends to decrease. As the carrier, those having the following magnetic properties are preferably used. That is, 79.57 kA / m (10
00 Oersted) is 30 to 3
It is preferable to use one having a pressure of 00 kA / m (30 to 300 emu / cm ³ ). If the intensity of magnetization of the carrier used is larger than 300 kA / m (300 emu / cm ³ ), it becomes difficult to obtain a high quality toner image. On the other hand, if it is less than ³⁰ kA / m (30 emu / cm ³ ), carrier adhesion is likely to occur because the magnetic binding force is reduced.

[0105]

EXAMPLES The specific structure of the toner of the present invention and the method for producing the same will be described below with reference to examples. [Example 1-1] <Preparation of toner particles serving as a base> In a four-necked flask equipped with a high-speed stirrer TK-homomixer, 910 parts by mass of ion-exchanged water and 100 parts by mass of polyvinyl alcohol were added. While stirring at 1200 rpm, 55
C. to obtain an aqueous dispersion medium. On the other hand, the following composition was dispersed for 3 hours using an attritor, and then 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added to prepare a monomer dispersion. . (Composition of monomer dispersion) ・ Styrene monomer 90 parts by mass ・ n-butyl acrylate monomer 30 parts by mass ・ Carbon black 10 parts by mass ・ Salicylic acid silane compound 1 part by mass ・ Release agent (paraffin wax 155) 20 parts by mass Department

Next, the obtained monomer dispersion liquid was charged into the dispersion medium in the four-necked flask, and granulation was performed for 10 minutes while maintaining the above rotation speed. Then, 50r
under stirring at 55 ° C. for 1 hour, then at 65 ° C.
For 4 hours and further at 80 ° C. for 5 hours. After the completion of the above polymerization, the slurry was cooled, and the dispersant was removed by repeating washing with purified water. Further, by performing washing and drying, toner particles serving as a base of the black toner were obtained. Using a Hitachi S-4500 Field Emission Scanning Electron Microscope, take a 5000x photo of the toner and measure the particle size from the photo so that the cumulative number is 300 or more. Calculated, 8.3
It was 0 μm. Further, from this result, the standard deviation (SD) of the number average particle diameter was calculated using a computer,
From this, the variation coefficient of the number distribution of the toner was calculated by the following equation. As a result, the variation coefficient of this toner is 3
It was 8.4%.

(Equation 3)

<Preparation of Coating Layer Consisting of Particles Containing at least Polycondensate of Silicon Compound> 0.9 parts by mass of the above-obtained black toner particles serving as a matrix were prepared by adding methanol to 4.
After dispersing in 1 part by mass, 2.5 as a silicon compound,
Parts by mass of tetraethoxysilane were dissolved, and further 40 parts by mass of methanol were added. The solution was then added to 28
By adding dropwise to an alkaline solution obtained by mixing 100 parts by mass of methanol with respect to 10 parts by mass of an aqueous NH ₄ OH solution of 10% by mass and stirring at room temperature for 48 hours, at least a polycondensate of a silicon compound is contained. A film composed of the particles was deposited on the surface of the toner particles.

After completion of the reaction, the obtained particles are washed with purified water and then with methanol, and then the particles are separated by filtration and dried to obtain a coating composed of particles containing at least a polycondensate of a silicon compound. The toner covered by the layer is obtained. When the particle size of the obtained toner was measured by the above-mentioned method, the number average particle size was 8.33 μm.
Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Furthermore, the abundance ratio of silicon atoms on the particle surface of the toner determined by EPMA was 15.32.
% By mass. Similarly, the proportion of silicon atoms in the cross section of the toner particles was 0.03%. Therefore, the abundance ratio of silicon atoms on the surface of the toner particles was 510.67 times the abundance ratio of silicon atoms on the cross section of the toner particles, and there was almost no polycondensate of the silicon compound inside the toner particles. . Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the ratio of silicon atoms present on the surface of the toner particles was 1%.
It was 1.44%. Therefore, the reduction rate of silicon atoms present on the surface of the toner particles before and after washing with the surfactant was 25.33%. Therefore, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular lumps were fixed.

Subsequently, 5 parts by mass of the toner and a particle size of 4
A two-component developer was prepared by mixing 95 parts by mass of carrier particles obtained by coating a silicone resin on a ferrite core of 0 μm. When the charge amount of the toner of the two-component developer was measured by the following method, it was -32.60 mC / kg. The method of measuring the charge amount of the toner is as follows.

10 g of the above two-component developer is placed in a 50 ml polybin, shaken with a shaker for 10 minutes, and charged. This blow-off powder charge measuring device (Toshiba Chemical Co. TB-200), mesh 625 mesh, blowing gas N _2, pressure: 9.81 × 10 ^-2 MP
a (1 kgf / cm ² ), and the value after 30 seconds is defined as the charge amount (mC / kg) of the toner. Further, using the above-mentioned developer, the full color laser copier copying machine CLC manufactured by Canon in an environment of a temperature of 25 ° C. and a humidity of 30% Rh.
700 remodeling machine (process speed 200mm / sec
And the transfer current in a 25 ° C./30% Rh environment is 40
0 μA) to form an image,
The toner performance was evaluated in the following manner. Further, 30,000 sheets were subjected to a durability test using the same machine. When the charge amount of the toner of the two-component developer after the durability test was measured,
It was 32.10 mC / kg, and it was confirmed that a stable charge amount was maintained even during durability.

Image Evaluation (1) Fixability After a solid image was copied on an OHP sheet, a part of the obtained image was cut out, and the image was cut using a scanning microscope.
Observation was carried out at a magnification of 00 to evaluate whether or not the toner particle shape remained. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well.

(2) Transfer Efficiency During the printing operation, the operation of the apparatus is stopped at the stage where all the transfer operations have not yet been completed, and the amount of toner (A) on the photoconductor before transfer is measured first. When the transfer was completed, the amount of toner (B) remaining on the photosensitive member without being transferred to the recording medium was measured, and the transfer efficiency was calculated by the following equation.

(Equation 4) As a result, the transfer efficiency of the toner of this example was 98.5%, and it was confirmed that the toner was transferred in a good state.

(3) Observation of Toner Particle Surface After Durability Test The toner particle surface after the durability test was observed with a scanning microscope photograph. The formed film was not damaged and maintained a surface state equivalent to that of the toner particles before the durability test.

Example 1-2 <Preparation of Base Toner Particles> Base toner particles were prepared by a pulverization method using the following method.・ Styrene / butyl acrylate = 80/20 copolymer 100 parts by mass ・ Carbon black 6 parts by mass ・ Chromium complex salt of di-tert-butylsalicylic acid 4 parts by mass After sufficiently premixing the above composition, melt-kneading, After cooling, it was roughly pulverized to a particle size of about 1 to 2 mm using a hammer mill. Next, it was pulverized by a pulverizer using an air jet method. Further, the obtained finely pulverized product was classified using an elbow jet classifier. In the same manner as in Example 1-1,
Using a Hitachi S-4500 Field Emission Scanning Electron Microscope, take a 5000x photo of the toner and measure the particle size from the photo so that the cumulative number is 300 or more. As a result of calculation, it was 8.9 μm.

<Preparation of Coating Layer Consisting of Particles Containing at least Silicon Compound Polycondensate> The procedure of Example 1-1 was repeated, except that the black toner particles obtained above were used as the base toner particles. A toner coated with a coating layer composed of particles containing at least a polycondensate of a silicon compound was obtained. The particle diameter of the obtained toner was determined in Example 1-1.
The number average particle diameter was measured by the same method as described above.
μm. Observation of the particle surface of this toner with a scanning microscope photograph revealed that the particle surface of the toner was approximately 40 nm.
A coating layer having fine granular irregularities with a fine diameter was observed. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the silicon atom abundance ratio on the particle surface of the toner determined by EPMA was 15.24.
% By mass. The content of silicon atoms in the cross section of the toner particles, measured in the same manner, was 0.02%. Therefore, the abundance ratio of silicon atoms on the surface of the toner particles was 762.00 times the abundance ratio of silicon atoms on the cross section of the toner particles, and almost no polycondensate of the silicon compound was present inside the toner particles. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 11.66%. Accordingly, the reduction rate of silicon atoms present on the surface of the toner particles before and after the surfactant was washed was 23.49%. Thus, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular mass was fixed.

Subsequently, using the obtained toner, a two-component developer was prepared in the same manner as in Example 1-1. When the charge amount of the toner of the two-component developer was measured, it was -33.40 mC / kg. Further, when the image evaluation using this developer was performed in the same manner as described in Example 1-1, the following results were obtained. When the charge amount of the toner of the two-component developer after the durability test was measured, it was -32.80 mC / kg, and it was confirmed that a relatively stable charge amount was maintained even during durability.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well.

(2) Transfer efficiency The transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 98.2%,
It was confirmed that the image was transferred in a good condition.

(3) Observation of Toner Particle Surface After Durability Test The toner particle surface after the durability test was observed by a scanning microscope photograph in the same manner as in Example 1-1. In the film composed of the particles containing the polycondensate of the silicon compound, a slightly damaged portion was confirmed, but it was of no problem.

[Example 1-3] Example 1 was dissolved in a mixed solvent obtained by dissolving 0.02 parts by mass of polyvinyl alcohol in 20 parts by mass of a mixed solution of ethanol / water = 1: 1 (mass ratio).
In -1, 0.9 parts by mass of the same black toner particles as the toner particles used as the base were dispersed, and then 5 parts by mass of 3- (methacryloxy) propyltrimethoxysilane was dissolved as a silicon compound. Subsequently, the solubility of the silicon compound was lowered by gradually dropping 120 parts by mass of water, and after the dropping was completed, stirring was further performed for 5 hours.
3- (methacryloxy) propyltrimethoxysilane was swollen into the toner particles.

Next, in this system, 28% by mass of NH ₄ O was added.
By adding 20 parts by mass of an H aqueous solution and stirring at room temperature for 12 hours, a sol-gel reaction was advanced on the surface of the toner particles to form a film composed of particles containing at least a polycondensate of a silicon compound. After the completion of the reaction, the obtained black powder is washed with ethanol to wash unreacted silicon compounds inside the particles, and further separated by filtration and dried to constitute particles containing at least a silicon compound polycondensate. To obtain a toner coated with a film.

When the particle size of the toner obtained above was measured by the method described above, the weight average particle size was 8.32 μm. Observation of the toner particles with a scanning microscope photograph revealed that a film having fine granular irregularities having a diameter of about 40 nm was formed on the surface of the toner particles. Further, transmission electron micrograph observation of the cut surface of the toner particles confirmed that a coating layer was formed on the surface of the toner particles.

Further, the abundance ratio of silicon atoms on the particle surface of the toner determined by EPMA was 3.33% by mass. The content ratio of silicon atoms in the particle cross section of the toner measured in the same manner was 0.25%. Therefore, the silicon atom abundance ratio on the toner particle surface was 13.32 times the silicon atom abundance ratio on the toner particle cross section, and the polycondensate of the silicon compound inside the toner particle was slight. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the particle surface of the toner was 2.98.
%Met. Therefore, the reduction rate of silicon atoms present on the toner particle surface before and after the surfactant cleaning is 10.5.
1%. Therefore, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular lumps were fixed.

Using the above toner, a two-component developer was prepared in the same manner as in Example 1-1. When the charge amount of the toner of the two-component developer was measured, it was -30.2 mC /
kg. Further, when the image evaluation using this developer was performed in the same manner as described in Example 1-1, the following results were obtained. The charge amount of the toner of the two-component developer after the durability test was -30.1
The charge amount was 8 mC / kg, and a stable charge amount was maintained even during durability as in Example 1-1.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well.

(2) Transfer efficiency The transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 98.4%,
It was transferred in a good condition.

(3) Observation of Particle Surface of Toner after Durability Test The surface of the toner particle after the durability test was observed by a scanning microscope photograph in the same manner as in Example 1-1. The film composed of the particles containing the polycondensate of the silicon compound was not broken, and the surface state equivalent to that of the toner particles before the durability test was maintained.

Example 1-4 4 parts by mass of dibutyl phthalate was finely dispersed in 120 parts by mass of a 0.3% by mass aqueous solution of sodium dodecylsulfonate using an ultrasonic homogenizer to prepare a dibutyl phthalate emulsion. Next, 0.9 parts by mass of the same black toner particles as used as the base in Example 1-1 were dispersed in 4.0 parts by mass of a 0.3% by mass aqueous solution of sodium dodecylsulfonate to prepare a dispersion of toner particles. Prepared. Thereafter, the above-obtained dibutyl phthalate emulsion was put into a dispersion of toner particles, and stirred at room temperature for 2 hours.

Next, 5 parts by mass of 3- (methacryloxy) propyltrimethoxysilane as a silicon compound was added to 100 parts by mass of a 0.3% by mass aqueous solution of sodium dodecylsulfonate, and finely dispersed using an ultrasonic homogenizer. The dispersion thus obtained is added to the dispersion of the toner particles obtained above, and the mixture is stirred at room temperature for 4 hours to disperse the parent toner particles and the silicon compound, and give 3- (methacryloxy)
The propyltrimethoxysilane was absorbed by the toner particles, and a silicon compound was introduced into the toner particles.

Thereafter, a 30% by mass aqueous NH ₄ OH solution 1
0 parts by mass was added, and the mixture was stirred at room temperature for 12 hours, and a sol-gel reaction was performed on the surface of the toner particles to form a film composed of particles containing at least a polycondensate of a silicon compound on the surface of the toner particles. After completion of the reaction, a large amount of ethanol was charged into the system to remove unreacted 3- (methacryloxy) propyltrimethoxysilane and dibutyl phthalate inside the particles. Next, the obtained toner particles were washed again with ethanol, subsequently, washed with purified water, separated by filtration, and dried to obtain the toner of this example.

When the particle size of the obtained toner was measured by the above-mentioned method, the weight average particle size was 8.69 μm. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the particle surfaces of the toner determined by EPMA was 3.42% by mass. Similarly, the proportion of silicon atoms in the particle cross section of the toner was 0.25%. Therefore,
The abundance ratio of silicon atoms on the surface of the toner particles is 13.13 of the abundance ratio of silicon atoms on the cross section of the toner particles.
The ratio was 68 times, and the presence of the polycondensate of the silicon compound inside the toner particles was slight. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the particle surface of the toner was 3.04%. Therefore, the reduction rate of silicon atoms existing on the particle surface of the toner before and after the washing of the surfactant was 11.11%. Thus, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular mass was fixed.

Using the above toner, a two-component developer was prepared in the same manner as in Example 1-1. When the charge amount of the toner of the two-component developer was measured, it was -29.64 mC.
/ Kg. When the image evaluation using this developer was performed in the same manner as described in Example 1-1 above, the following results were obtained. The charge amount of the toner of the two-component developer after the durability test was -29.60 m.
C / kg, and the charge amount was stably maintained by the endurance as in Example 1-1.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well.

(2) Transfer efficiency The transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 98.4%,
It was transferred in a good condition.

(3) Observation of Particle Surface of Toner after Durability Test The surface of the toner particle after the durability test was observed by a scanning microscope photograph in the same manner as in Example 1-1. The film composed of the particles containing the polycondensate of the silicon compound was not broken, and the surface state equivalent to that of the toner particles before the durability test was maintained.

[Example 1-5] 2 parts by mass of isoamyl acetate and 3.5 parts of tetraethoxysilane as a silicon compound
After mixing a mixed solution obtained by mixing 0.5 parts by mass of methyltriethoxysilane with 30 parts by mass of an aqueous solution of 0.3% by mass of sodium dodecylbenzenesulfonate, the mixture was stirred using an ultrasonic homogenizer, A mixed dispersion of isoamyl acetate, tetraethoxysilane, and methyltriethoxysilane was prepared. Then, Example 1-1
In a dispersion obtained by dispersing 0.9 parts by mass of the same black toner particles used as a base in 30 parts by mass of a 0.3% by mass aqueous solution of sodium dodecylbenzenesulfonate, the above-obtained isoamyl acetate and silicon compound were mixed. The mixed dispersion was charged and stirred at room temperature for 2 hours to introduce the silicon compound into the toner particles.

Next, 5 parts by mass of an aqueous solution of 28% by mass of NH ₄ OH are mixed, and the mixture is stirred at room temperature for 12 hours to carry out a sol-gel reaction. A structured film was formed. Next, a large amount of ethanol is charged into the system, and unreacted tetraethoxysilane, methyltriethoxysilane, and isoamyl acetate are removed from the inside of the toner particles.
After further washing the particles with ethanol, washing with purified water,
The toner was obtained by filtration and drying.

When the particle size of the toner obtained above was measured by the method described above, the weight average particle size was 8.74 μm. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron micrograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the particle surface of the toner determined by EPMA was 3.15% by mass. Similarly, the proportion of silicon atoms present in the cross section of the toner particles was 0.33%. Therefore,
The abundance ratio of silicon atoms on the surface of the toner particles is 9.5 of the abundance ratio of silicon atoms on the cross section of the toner particles.
5 times, and the presence of the polycondensate of the silicon compound inside the toner particles was slight. Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the particle surface of the toner was 2.98%. Therefore, the reduction rate of silicon atoms existing on the surface of the toner particles before and after the washing of the surfactant was 5.40%. Therefore, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular lumps were fixed.

Using the above toner, a two-component developer was prepared in the same manner as in Example 1-1. When the charge amount of the toner of the two-component developer was measured, it was -28.24 mC
/ Kg. When the image evaluation using this developer was performed in the same manner as described in Example 1-1 above, the following results were obtained. The charge amount of the toner of the two-component developer after the durability test was -28.21 m.
C / kg, and the charge amount was stably maintained by the endurance as in Example 1-1.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well.

(2) Transfer efficiency The transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 98.4%,
It was transferred in a good condition.

(3) Observation of Toner Particle Surface After Durability Test The toner particle surface after the durability test was observed by a scanning microscope photograph in the same manner as in Example 1-1. The film composed of the particles containing the polycondensate of the silicon compound was not broken, and the surface state equivalent to that of the toner particles before the durability test was maintained.

(4) Scattering The degree of scattering of the toner image formed on the drum was visually evaluated, and it was found that scattering was slightly larger than the original toner particles.

[Example 1-6] In Example 1-5, a dispersion of a silicon compound was added to a dispersion of toner particles. The method of adding a dispersion of toner particles to a dispersion of silicon compound was used. The toner of this example was obtained in exactly the same manner except for the change.

When the particle size of the obtained toner was measured by the above-mentioned method, the weight average particle size was 8.49 μm, and the coefficient of variation of the particles was 38.8%, which was almost the same as the original toner particles. The coefficient of variation is shown. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the particle surface of the toner determined by EPMA was 3.75% by mass. Similarly, the abundance ratio of silicon atoms in the particle cross section of the toner was 0.31%. Therefore,
The abundance ratio of silicon atoms on the particle surface of the toner is represented by 12.13.
The ratio was 10 times, and the presence of a polycondensate of a silicon compound inside the toner particles was slight. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the particle surface of the toner was 3.63%. Therefore, the reduction ratio of the ratio present on the toner particle surface before and after the surfactant was washed was 3.20%. Therefore, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular lumps were fixed.

Using the above toner, a two-component developer was prepared in the same manner as in Example 1-1. The charge amount of the toner of the two-component developer was measured to be −31.80 mC.
/ Kg. When the image evaluation using this developer was performed in the same manner as described in Example 1-1 above, the following results were obtained. The charge amount of the toner of the two-component developer after the durability test was −31.78 m.
C / kg, and the charge amount was stably maintained by the endurance as in Example 1-1.

(1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well.

(2) Transfer efficiency The transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 97.5%,
It was transferred in a good condition.

(3) Observation of Particle Surface of Toner after Durability Test The surface of the toner particle after the durability test was observed with a scanning microscope photograph in the same manner as in Example 1-1. The film composed of the particles containing the polycondensate of the silicon compound was not broken, and the surface state equivalent to that of the toner particles before the durability test was maintained.

(4) Scattering The degree of scattering of the toner image on the drum was visually evaluated, and the degree of scattering was about the same as the original particles.

[Example 1-7] The toner obtained in Example 1-1 was used as a one-component developer and charged in a commercially available electrophotographic copying machine FC-2 (manufactured by Canon Inc.). Under an environment of a temperature of 25 ° C. and a humidity of 30% Rh, a durability test was performed using 30,000 sheets of solid white images, and the same evaluation as in Example 1-1 was performed. The following results were obtained.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well.

(2) Transfer Efficiency Transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 98.6%,
It was transferred in a good condition.

(3) Observation of Toner Particle Surface After Durability Test The toner particle surface after the durability test was observed in the same manner as in Example 1-1. The film composed of particles containing the polycondensate of No. 1 was not broken, and maintained a surface state equivalent to that of the toner particles before the durability test.

The charge amount of the toner used as the one-component developer was measured by the following method.
C / kg, and the charge amount of the one-component developer (toner) after the endurance test of 30,000 sheets is -30.30 mC / kg,
The charge amount was stable even after running.

The method of measuring the charge amount of the toner is as follows. Iron powder carrier (EFV-100 / 200)
9.5 g and 0.5 g of the toner are put in a 50 ml poly bottle, shaken with a shaker for 10 minutes, and charged. This is a blow-off powder charge meter (Toshiba Chemical Co., Ltd.)
TB-200), the mesh is 625 mesh, blowing gas N ₂ , pressure: 9.81 × 10 ^-2 MPa (1 kgf).
/ Cm ² ), and the value after 30 seconds is defined as the charge amount of the toner.

Example 1-8 As a monomer dispersion,
In the composition of the monomer dispersion used in Example 1-1, 5 parts by mass of tetraethoxysilane was further added as a silicon compound, and an NH ₄ OH aqueous solution was added to the system, and the monomer dispersion was added. The polymerization was carried out in the same manner as the polymerization method of Example 1-1 except that the polymerization was made alkaline. As a result, the silicon compound contained in the toner particles during the production of the polymerized toner tends to cause a sol-gel reaction by heat. Thereafter, the film was washed with a large amount of ethanol to remove unreacted tetraethoxysilane inside the particles, and further filtered and dried to provide a film composed of particles containing at least a polycondensate of a silicon compound. A toner was obtained.

When the particle size of the toner was measured by the above-mentioned method, the weight average particle size was 8.65 μm. When the particle surface of this toner was observed with a scanning microscope photograph,
A coating layer having fine granular irregularities with a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content of silicon atoms on the particle surface of the toner determined by EPMA was 10.12.
% By mass. Similarly, the abundance ratio of silicon atoms in the particle cross section of the toner was 5.75%. Therefore, the abundance ratio of silicon atoms on the particle surface of the toner is 1.76 times the abundance ratio of silicon atoms on the cross section of the toner particle, and a polycondensate of the silicon compound exists inside the toner particle. It was confirmed that. Furthermore,
After the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the particle surface of the toner was 9.84%. Therefore, the reduction rate of silicon atoms present on the surface of the toner particles before and after the surfactant was washed was 2.77%. Therefore, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular lumps were fixed.

Using the above toner, a two-component developer was prepared in the same manner as in Example 1-1. When the charge amount of the toner of the two-component developer was measured, it was -33.24 mC.
/ Kg. When the image evaluation using this developer was performed in the same manner as described in Example 1-1 above, the following results were obtained. The charge amount of the toner of the two-component developer after the durability test is -32.84 mC / kg.
And was stable even after endurance.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, the particle shape of the developer was partially observed, and it was confirmed that the fixability was inferior to those of the other examples. However, the whole was smooth and there was no practical problem.

(2) Transfer Efficiency Transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 98.5%,
It was transferred in a good condition.

(3) Observation of Particle Surface of Toner after Durability Test The surface of the toner particle after the durability test was observed with a scanning microscope photograph in the same manner as in Example 1-1. The film composed of the particles containing the polycondensate of the silicon compound was not broken, and the surface state equivalent to that of the toner particles before the durability test was maintained.

[Example 1-9] In Example 1-1,
When performing a sol-gel reaction, a film composed of particles containing at least a polycondensate of a silicon compound is provided in the same manner as in Example 1-1, except that the amount of tetraethoxysilane was set to 0.5 parts by mass. Toner was obtained.

When the particle size of this toner was measured by the method described above, the weight average particle size was 8.35 μm. When the particle surface of this toner was observed with a scanning microscope photograph,
A coating layer having fine granular irregularities with a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content of silicon atoms on the particle surface of the toner obtained by EPMA was 0.08% by mass. Similarly, the abundance ratio of silicon atoms in the toner particle cross section was 0.01%. Therefore,
The abundance ratio of silicon atoms on the particle surface of the toner is 8.0 of the abundance ratio of silicon atoms on the cross section of the toner particles.
It was 0 times. Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the particle surface of the toner was 0.06%. Therefore,
The reduction rate of silicon atoms present on the surface of the toner particles before and after washing with the surfactant was 25.00%. Therefore, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular lumps were fixed.

Using the toner described above, a two-component developer was prepared in the same manner as in Example 1-1. The charge amount of the toner of the two-component developer was measured to be -26.01 mC.
/ Kg. When the image evaluation using this developer was performed in the same manner as described in Example 1-1 above, the following results were obtained. The charge amount of the toner of the two-component developer after the durability test is -25.51 mC / kg.
And was stable even after endurance.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape of the toner was observed, and the toner was well fixed.

(2) Transfer Efficiency Transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 97.2%,
It was transferred in a good condition.

(3) Observation of Particle Surface of Toner after Durability Test The surface of the toner particle after the durability test was observed by a scanning microscope photograph in the same manner as in Example 1-1. The film composed of the particles containing the polycondensate of the silicon compound was not broken, and the surface state equivalent to that of the toner particles before the durability test was maintained.

[Example 1-10] The procedure of Example 1-1 was repeated, except that the amount of tetraethoxysilane was changed to 6.0 parts by mass when the sol-gel reaction was carried out. A toner provided with a film composed of particles containing at least a polycondensate of a silicon compound was obtained.

When the particle size of the obtained toner was measured by the above-mentioned method, the weight average particle size was 8.79 μm. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content ratio of silicon atoms on the particle surface of the toner determined by EPMA was 10.33.
% By mass. Similarly, the abundance ratio of silicon atoms in the particle cross section of the toner was 0.04%. Therefore, the abundance ratio of silicon atoms on the particle surface of the toner is 258.25 times the abundance ratio of silicon atoms on the particle cross section of the toner, and a large amount of a polycondensate of a silicon compound is present on the particle surface. confirmed. Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the existing ratio of silicon atoms on the particle surfaces of the toner was 7.66%. Therefore, the reduction rate of silicon atoms present on the surface of the toner particles before and after the surfactant was washed was 25.85%. Therefore, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular lumps were fixed.

Using the above toner, a two-component developer was prepared in the same manner as in Example 1-1. The charge amount of the toner of the two-component developer was measured to be −33.59 mC.
/ Kg. When the image evaluation using this developer was performed in the same manner as described in Example 1-1 above, the following results were obtained. The charge amount of the toner of the two-component developer after the durability test is −32.99 mC / kg.
And was stable even after endurance.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, the particle shape of the developer was partially observed, and it was confirmed that the fixability was inferior to those of the other examples. However, the whole was smooth and there was no practical problem.

(2) Transfer Efficiency Transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 98.7%,
It was transferred in a good condition.

(3) Observation of Toner Particle Surface After Durability Test The toner particle surface after the durability test was observed by a scanning microscope photograph in the same manner as in Example 1-1. The film composed of the particles containing the polycondensate of the silicon compound was not broken, and the surface state equivalent to that of the toner particles before the durability test was maintained.

[Comparative Example 1-1] The black toner particles obtained in Example 1-1 were used as they were without forming a coating layer on the surface, in the same manner as in Example 1-1. To prepare a two-component developer. When the charge amount of the toner of the two-component current developer was measured, it was -10.4 mC / k
g. When the image evaluation using this developer was performed in the same manner as described in Example 1-1 above, the following results were obtained. The charge amount of the toner of the two-component developer after the durability test was −8.95 mC / kg, and the charge amount after the durability test was slightly reduced.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well.

(2) Transfer Efficiency Transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this comparative example was 68.9%, which was inferior to the example.

Comparative Example 1-2 To 100 parts by mass of the black toner particles obtained in Example 1-1, 5 parts by mass of a hydrophobic silica fine powder having a weight average particle size of 40 nm was added.
By mixing with a Henschel mixer, a toner was obtained in which silica fine powder was externally added as a fluidizing agent.

When the particle size of the toner obtained above was measured by the method described above, the weight average particle size was 8.33 μm. When this toner was observed with a scanning micrograph,
Although particulate matter was observed on the surface of the toner particles,
There were many gaps between the particles, and they did not form a film. Further, when the cross section of the toner was observed with a transmission electron microscope photograph, the presence of particles and a continuous layer were sometimes confirmed on the surface of the particles of the toner, but no continuous layer was confirmed.

The content ratio of silicon atoms on the particle surface of the toner determined by EPMA was 0.45% by mass. Similarly, the proportion of silicon atoms in the cross section of the toner particles was 0.00%. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the particle surface of the toner was 0.3%.
It was 0%. Therefore, the reduction rate of silicon atoms existing on the surface of the toner particles before and after the surfactant cleaning is 33.
33%. Therefore, this toner was not recognized as a fixed layer because the rate of silicon reduction by washing with a surfactant was high.

Using the toner described above, a two-component developer was prepared in the same manner as in Example 1-1. When the charge amount of the toner of the two-component developer was measured, it was −29.8 mC /
kg. Further, when the image evaluation using this developer was performed in the same manner as described in Example 1-1, the following results were obtained. The charge amount of the toner of the two-component developer after the durability test was −26.4.
mC / kg, which was slightly lower.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well.

(2) Transfer Efficiency Transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this comparative example was 89.7%,
It was slightly inferior to the example.

(3) Observation of Particle Surface of Toner After Durability Test The surface of the toner particle after the durability test was observed with a scanning microscope photograph in the same manner as in Example 1-1. It was separated in some places or embedded in the toner particles, and an increase in the gap between the silica particles was observed.

Table 1 summarizes the characteristics of the toner particles and the toner in Examples 1-1 to 1-10 and Comparative Examples 1-1 and 1-2. Table 2 collectively shows the results of the image evaluation test when the developers using the toners in Examples 1-1 to 1-10 and Comparative Examples 1-1 and 1-2 were used.

[0194]

[Table 1]

[0195]

[Table 2]

The fixability in the table is obtained by developing and fixing on an OHP sheet, and then observing the image at a magnification of 1000 with a scanning microscope, and evaluated as follows. A: No portion maintaining the toner particle shape is observed. B: Several portions maintaining the toner particle shape are present. C: Most portions maintain the toner particle shape.

Example 2-1 <Preparation of Base Toner Particles> In a four-necked flask equipped with a high-speed stirrer TK-homomixer, 910 parts by mass of ion-exchanged water and 100 parts by mass of polyvinyl alcohol were placed. While stirring at 1200 rpm.
C. to obtain an aqueous dispersion medium. On the other hand, the following composition was dispersed for 3 hours using an attritor, and then 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added to prepare a monomer dispersion. . (Composition of monomer dispersion liquid) ・ Styrene monomer 85 parts by mass ・ n-butyl acrylate monomer 35 parts by mass ・ Carbon black 12 parts by mass ・ Salicylic acid silane compound 1.5 parts by mass ・ Release agent 20 parts by mass

Next, the obtained monomer dispersion liquid was charged into the dispersion medium in the four-necked flask, and granulation was performed for 10 minutes while maintaining the above rotation speed. Then, 50r
under stirring at 55 ° C. for 1 hour, then at 65 ° C.
For 4 hours and further at 80 ° C. for 5 hours. After the completion of the above polymerization, the slurry was cooled, and the dispersant was removed by repeating washing with purified water. Further, by performing washing and drying, toner particles serving as a base of the black toner were obtained. Using a Hitachi S-4500 Field Emission Scanning Electron Microscope, take a 5000x photo of the toner and measure the particle size from the photo so that the cumulative number is 300 or more. Calculated, 8.3
It was 0 μm. Further, from this result, the standard deviation (SD) of the number average particle diameter was calculated using a computer,
From this, the variation coefficient of the number distribution was calculated. As a result, the variation coefficient of the toner particles was 38.4%.

<Preparation of Coating Layer Consisting of Particles Containing at least Silicon Compound Polycondensate> 0.9 parts by mass of the above-obtained black toner particles serving as a base were prepared by adding methanol to 3.
After dispersing in 5 parts by mass, 3.0 as a silicon compound was obtained.
The parts by mass of tetraethoxysilane and 0.5 parts by mass of methyltrimethoxysilane were dissolved, and 40 parts by mass of methanol was further added. Subsequently, this solution was added to 28% by mass.
Was added dropwise to an alkaline solution obtained by mixing 100 parts by mass of methanol with respect to 10 parts by mass of an aqueous NH ₄ OH solution, and the mixture was stirred at room temperature for 12 hours to remove particles containing at least silicon compound polycondensate. The resulting film was deposited on the surface of the toner particles.

Next, this reaction system is heated to 50 ° C., the evaporated material is cooled, and the ammonia is removed by removing the evaporated material outside the system. Thereafter, the liquid volume is reduced to the same level as before the heating. , And then gradually add acetic acid.
It continued adding until it became H2. Next, 0.2 parts by mass of dimethylethoxysilane was added to the system, and the mixture was stirred for 30 minutes to perform a coupling treatment. Then, filtration and washing were repeated, followed by drying to obtain a toner of this example. When the particle size of the obtained toner was measured by the above-mentioned method, the number average particle size was 8.65 μm. Observation of the particle surface of this toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 45 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content ratio of silicon atoms on the particle surface of the toner determined by EPMA was 16.32.
% By mass. Similarly, the abundance ratio of silicon atoms in the particle cross section of the toner was 0.03% by mass. Therefore, the abundance ratio of silicon atoms on the particle surface of the toner was 544 times the abundance ratio of silicon atoms on the cross section of the toner particle, and almost no polycondensate of the silicon compound was present inside the toner particle. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the surface of the toner particles was 15.3.
It was 4% by mass. Therefore, the reduction rate of silicon atoms present on the surface of the toner particles before and after the washing with the surfactant was 6.00%. Accordingly, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular lumps were fixed.

Subsequently, 5 parts by mass of the toner and a particle size of 4
A two-component developer was prepared by mixing 95 parts by mass of carrier particles obtained by coating a silicone resin on a ferrite core of 0 μm. When the charge amount of the toner of the obtained two-component developer was measured in an environment at a temperature of 25 ° C. and a humidity of 30% Rh, it was −32.46 mC / kg.

Further, using the two-component developer obtained above, Example 1 under an environment of a temperature of 25 ° C. and a humidity of 30% Rh.
-1 to form an image using the same full-color laser copier copying machine CLC700 modified by Canon as used in
The following items were evaluated for toner performance in the following manner. A 30,000-sheet durability test was performed by the same machine. When the charge amount of the toner of the two-component developer after the durability test was measured by the above method, it was -31.86 mC / kg, and it was confirmed that a stable charge amount was maintained even during durability. The image after the durability was good without any deterioration. Table 4 shows the evaluation results.

Image Evaluation (1) Fixability Evaluation was performed in the same manner as in Example 1-1. As a result, no particle shape was observed, and it was confirmed that the particles were fixed well. Table 4 shows the evaluation results.

(2) Transfer Efficiency Transfer efficiency was calculated in the same manner as in Example 1-1. As a result, the transfer efficiency of the toner of this embodiment is 98.6%,
It was confirmed that the image was transferred in a good condition.

(3) Observation of Toner Particle Surface After Durability Test The toner particle surface after the durability test was observed by a scanning microscope photograph in the same manner as in Example 1-1. The film composed of particles containing the polycondensate of No. 1 was not broken, and maintained a surface state equivalent to that of the toner particles before the durability test.

Further, the same evaluation as above was conducted at 30 ° C. and 80% humidity.
When the test was performed in an environment of% Rh, the charge amount of the toner in the initial stage of durability was -32.22 mC / kg, and the influence of the environmental change was small. The charge amount of the toner after the endurance of 30,000 sheets is-
31.74 mC / kg, and even under high temperature and high humidity,
No large decrease in the charge amount was observed before and after the endurance, and the obtained image was stable and good.

Example 2-2 A coating layer composed of particles containing a polycondensate of a silicon compound was provided in the same manner as in Example 2-1. Thereafter, filtration and washing were repeated, and filtration was performed. The particles were redispersed in 40 parts by weight of alcohol,
Coupling treatment was performed in the same manner as in Example 1 to obtain toner particles of this example. When the particle size of the toner was measured by the above-described method, the number average particle size was 8.45 μm.
Observation of the toner particles with a scanning micrograph revealed that
A film having fine granular irregularities on the surface of the toner particles was observed. Further, it was confirmed from the transmission electron microscope photograph of the cross section of the toner that a coating layer was formed on the surface of the toner. Furthermore, the number average particle diameter of the particles in the film on the surface of the toner particles was determined by measuring the diameter of fine particles on the surface from observation of the surface of the toner particles with a scanning electron microscope.

Further, the content of silicon atoms on the surface of the toner particles determined by EPMA was 15.98.
% By mass. The proportion of silicon atoms in the toner cross section measured in the same manner was 0.02% by mass. Therefore, the abundance ratio of silicon atoms on the particle surface of the toner was 799 times the abundance ratio of silicon atoms on the cross section of the toner particles, and the polycondensate of the silane compound was hardly present inside the toner particles.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the particle surface of the toner was 15.39% by mass. Therefore, the reduction rate of silicon atoms on the particle surface of the toner before and after the washing with the surfactant was 3.69%. Therefore, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which granular lumps were fixed.

Subsequently, using the obtained toner, a two-component developer was prepared in the same manner as in Example 2-1.
The charge amount of the toner of the component developer is 25 ° C. and the humidity is 30% R.
When measured under the environment of h, it was -31.15 mC / kg. Furthermore, using this developer, 25 ° C., humidity 30
In an environment of% Rh, an image is formed using a modified full-color laser copier copying machine CLC700 manufactured by Canon Inc.
A 30,000-sheet durability test was performed in the same manner as in Example 2-1. When the charge amount of the toner of the two-component developer after the durability test was measured, it was −30.77 mC / kg, and it was confirmed that a stable charge amount was maintained even during durability. The image after the durability test was satisfactory without any deterioration. Table 4 shows the results.

Further, the same measurement was conducted at 30 ° C. and 80% humidity.
When the test was performed in an environment of Rh, the charge amount in the initial stage of durability was -3.
0.86 mC / kg, the influence of environmental changes was small. The charge amount after 30,000-sheet running was -30.35 mC / kg. Even under high temperature and high humidity, the charge was not significantly reduced before and after running, and the image was good.

Example 2-3 A toner having a coating layer composed of particles containing a polycondensate of a silicon compound formed on the surface of toner particles was prepared in the same manner as in Example 2-1. After the layer was formed, the particles were sufficiently washed, separated by filtration, and dried to isolate toner particles. Next, a 25% methanol solution of dimethylethoxysilane was prepared, and the above methanol solution was sprayed at a ratio of 10 parts by mass with respect to 50 parts by mass of the toner obtained by the above-described method, while using a Henschel mixer for 20 minutes. The mixture was stirred, and then fluidized to prepare a toner. When the particle size of the toner was measured by the above-described method, the number average particle size was 8.82 μm. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities with a diameter of about 50 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content ratio of silicon atoms on the particle surface of the toner determined by EPMA was 15.87.
% By mass. Similarly, the abundance ratio of silicon atoms in the particle cross section of the toner was 0.03% by mass. Therefore, the abundance ratio of silicon atoms on the particle surface of the toner was 529 times the abundance ratio of silicon atoms on the cross section of the toner particle, and the polycondensate of the silicon compound was small inside the toner particle. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the surface of the toner particles was 15.28% by mass. Accordingly, the reduction rate of silicon atoms present on the surface of the toner particles before and after the cleaning with the surfactant is 3.72.
%Met. Thus, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular mass was fixed.

Subsequently, using the obtained toner, a two-component developer was prepared in the same manner as in Example 2-1.
The charge amount of the toner of the component developer is 25 ° C. and the humidity is 30% R.
When measured under the environment of h, it was −31.52 mC / kg. Furthermore, using this developer, 25 ° C., humidity 30
In an environment of% Rh, an image is formed using a modified full-color laser copier copying machine CLC700 manufactured by Canon Inc.
A 30,000-sheet durability test was performed in the same manner as in Example 2-1. When the charge amount of the toner of the two-component developer was measured after the durability test, it was −31.13 mC / kg, and it was confirmed that a stable charge amount was maintained even during durability. The image after the durability test was satisfactory without any deterioration.

Further, the same measurement was conducted at 30 ° C. and 80% humidity.
When the test was performed in an environment of Rh, the charge amount in the initial stage of durability was -3.
1.33 mC / kg, the influence of environmental changes was small. The charge amount after 30,000-sheet running was -30.86 mC / kg, and even under high temperature and high humidity, the charge was not significantly reduced before and after running, and the image was good. Table 4 shows the results.

[Example 2-4] In the same manner as in the production method of Example 2-1 except that the coupling agent was changed to titanium ethoxide, a silicon-containing material treated with a titanium coupling agent was used. A toner having a coating layer was obtained. When the particle size of this toner was measured by the above-described method, the number average particle size was 8.69 μm. Observation of the particle surface of this toner with a scanning microscope photo revealed that a coating layer having fine granular irregularities having a diameter of about 46 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Furthermore, the abundance ratio of silicon atoms on the particle surface of the toner determined by EPMA was 13.55.
% By mass. Similarly, the abundance ratio of silicon atoms in the particle cross section of the toner was 0.03% by mass. Therefore, the abundance ratio of silicon atoms on the particle surfaces of the toner was 452 times the abundance ratio of silicon atoms on the cross section of the toner particles, and the polycondensate of the silicon compound was small inside the toner particles. Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the surface of the toner particles was 12.56% by mass. Therefore, the reduction rate of silicon atoms present on the surface of the toner particles before and after washing with the surfactant is 7.31.
%Met. Thus, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular mass was fixed.

Subsequently, using the obtained toner, a two-component developer was prepared in the same manner as in Example 2-1.
The charge amount of the toner of the component developer is 25 ° C. and the humidity is 30% R.
When measured under the environment of h, it was -33.21 mC / kg. Furthermore, using this developer, 25 ° C., humidity 30
In an environment of% Rh, an image is formed using a modified full-color laser copier copying machine CLC700 manufactured by Canon Inc.
A 30,000-sheet durability test was performed in the same manner as in Example 2-1. When the charge amount of the toner of the two-component developer after the durability test was measured, it was -32.77 mC / kg, and it was confirmed that a stable charge amount was maintained even during the durability. The image after the durability test was satisfactory without any deterioration.

Further, the same measurement was carried out at 30 ° C. and 80% humidity.
When the test was performed in an environment of Rh, the charge amount in the initial stage of durability was -3.
3.00 mC / kg, the influence of environmental changes was small. The charge amount after the 30,000-sheet running was -32.48 mC / kg. Even under high temperature and high humidity, the charge amount did not significantly decrease before and after the running, and the image was good. Table 4 shows the results.

[Example 2-5] In the method for producing a toner of Example 2-1, the coupling agent was changed to aluminum (II).
I) A toner treated with a silicon-containing coating layer treated with an aluminum coupling agent was obtained in the same manner except that n-butoxide was used. When the particle size of this toner was measured by the method described above, the number average particle size was 8.74 μm.
m. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 48 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content ratio of silicon atoms on the particle surface of the toner determined by EPMA was 12.54.
% By mass. Similarly, the proportion of silicon atoms in the particle cross section of the toner was 0.02% by mass. Therefore, the abundance ratio of silicon atoms on the particle surface of the toner was 627 times the abundance ratio of silicon atoms on the cross section of the toner particle, and the polycondensate of the silicon compound was small inside the toner particle. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the surface of the toner particles was 11.57% by mass. Therefore, the reduction rate of the silicon atoms present on the particle surface of the toner before and after washing with the surfactant is 7.74.
%Met. Thus, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular mass was fixed.

Subsequently, a two-component developer was prepared by using the obtained toner in the same manner as in Example 2-1.
The charge amount of the toner of the component developer is 25 ° C. and the humidity is 30% R.
When measured under the environment of h, it was -33.25 mC / kg. Furthermore, using this developer, 25 ° C., humidity 30
In an environment of% Rh, an image is formed using a modified full-color laser copier copying machine CLC700 manufactured by Canon Inc.
A 30,000-sheet durability test was performed in the same manner as in Example 2-1. When the charge amount of the toner of the two-component developer after the durability test was measured, it was -32.90 mC / kg, and it was confirmed that a stable charge amount was maintained even during the durability. The image after the durability test was satisfactory without any deterioration. Furthermore, when the same measurement was performed in an environment of 30 ° C. and a humidity of 80% Rh, the charge amount at the beginning of the endurance was −30.92 mC /
kg and the effects of environmental changes were small. The charge amount after 30,000-sheet running was −30.40 mC / kg, and even under high temperature and high humidity, the charge was not significantly reduced before and after running, and the image was good. Table 4 shows the results.

[Example 2-6] Silane-coupling-containing silicon was produced in the same manner as in Example 2-1 except that the coupling agent was changed to methacryloxypropylmethyldimethoxysilane. A toner covered with the coating layer was obtained. When the particle size of this toner was measured by the above-described method, the number average particle size was 8.69 μm.
Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 48 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content ratio of silicon atoms on the particle surface of the toner determined by EPMA was 16.54.
% By mass. Similarly, the abundance ratio of silicon atoms in the particle cross section of the toner was 0.03% by mass. Therefore, the abundance ratio of silicon atoms on the particle surface of the toner was 551 times the abundance ratio of silicon atoms on the cross section of the toner particles, and the polycondensate of the silicon compound was small inside the toner particles. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the surface of the toner particles was 15.67% by mass. Therefore, the reduction rate of silicon atoms present on the surface of the toner particles before and after washing with the surfactant is 5.26.
%Met. Thus, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular mass was fixed.

Subsequently, a two-component developer was prepared using the obtained toner in the same manner as in Example 2-1.
The charge amount of the toner of the component developer is 25 ° C. and the humidity is 30% R.
When measured under the environment of h, it was -31.41 mC / kg. Furthermore, using this developer, 25 ° C., humidity 30
In an environment of% Rh, an image is formed using a modified full-color laser copier copying machine CLC700 manufactured by Canon Inc.
A 30,000-sheet durability test was performed in the same manner as in Example 2-1. When the charge amount of the toner of the two-component developer was measured after the durability test, it was -31.01 mC / kg, and it was confirmed that a stable charge amount was maintained even during durability. The image after the durability test was satisfactory without any deterioration.

Further, the same measurement was conducted at 30 ° C. and 80% humidity.
When the test was performed in an environment of Rh, the charge amount in the initial stage of durability was -3.
3.76 mC / kg, the influence of environmental changes was small. The charge amount after 30,000-sheet running was -33.23 mC / kg. Even under high temperature and high humidity, the charge was not significantly reduced before and after running, and the image was good. Table 4 shows the results.

[Example 2-7] A target toner was obtained in the same manner as in Example 2-1 except that the coupling agent in Example 2-1 was changed to hexamethyldisilazane. When the particle size of the toner was measured by the above-described method, the number average particle size was 8.82 μm. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities with a diameter of about 50 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the particle surface of the toner determined by EPMA was 16.25.
% By mass. Similarly, the abundance ratio of silicon atoms in the particle cross section of the toner was 0.03% by mass. Therefore, the abundance ratio of silicon atoms on the particle surface of the toner was 542 times the abundance ratio of silicon atoms on the cross section of the toner particles, and the polycondensate of the silicon compound was small inside the toner particles. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the surface of the toner particles was 15.41% by mass. Accordingly, the reduction rate of silicon atoms present on the surface of the toner particles before and after the cleaning with the surfactant is 5.17.
%Met. Thus, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular mass was fixed.

Subsequently, using the obtained toner, a two-component developer was prepared in the same manner as in Example 2-1.
The charge amount of the toner of the component developer is 25 ° C. and the humidity is 30% R.
When measured under the environment of h, it was -32.11 mC / kg. Furthermore, using this developer, 25 ° C., humidity 30
In an environment of% Rh, an image is formed using a modified full-color laser copier copying machine CLC700 manufactured by Canon Inc.
A 30,000-sheet durability test was performed in the same manner as in Example 2-1. When the charge amount of the toner of the two-component developer after the durability test was measured, it was -31.69 mC / kg, and it was confirmed that a stable charge amount was maintained even during the durability. The image after the durability test was satisfactory without any deterioration.

Further, the same measurement was conducted at 30 ° C. and 80% humidity.
When the test was performed in an environment of Rh, the charge amount in the initial stage of durability was -3.
1.89 mC / kg, the influence of environmental changes was small. The charge amount after 30,000-sheet running was -31.43 mC / kg, and even under high temperature and high humidity, the charge was not significantly reduced before and after running, and the image was good. Table 4 shows the results.

Example 2-8 A target toner was obtained in the same manner as in Example 2-1 except that dimethylethoxysilane was used as a coupling agent in an amount of 2.0 parts by mass. When the particle size of this toner was measured by the method described above, the number average particle size was 8.99 μm. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities of about 54 nm in diameter was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content of silicon atoms on the particle surface of the toner determined by EPMA was 17.02.
% By mass. Similarly, the proportion of silicon atoms in the particle cross section of the toner was 0.02% by mass. Therefore, the silicon atom abundance ratio on the toner particle surface was 851 times the silicon atom abundance ratio on the toner particle cross section, and it was confirmed that a silicon compound polycondensate was present inside the toner particle. Was done.

Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the surface of the toner particles was 16.24% by mass. Therefore, the reduction rate of silicon atoms present on the particle surface of the toner before and after washing with the surfactant was 4.58%. Thus, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular mass was fixed.

Subsequently, using the obtained toner, a two-component developer was prepared in the same manner as in Example 2-1.
The charge amount of the toner of the component developer is 25 ° C. and the humidity is 30% R.
When measured under the environment of h, it was -33.24 mC / kg. Furthermore, using this developer, 25 ° C., humidity 30
In an environment of% Rh, an image is formed using a modified full-color laser copier copying machine CLC700 manufactured by Canon Inc.
A 30,000-sheet durability test was performed in the same manner as in Example 2-1. When the charge amount of the toner of the two-component developer after the durability test was measured, it was -32.65 mC / kg, and it was confirmed that a stable charge amount was maintained even during the durability. The image after the durability test was satisfactory without any deterioration.

Further, the same measurement was conducted at 30 ° C. and 80% humidity.
When the test was performed in an environment of Rh, the charge amount in the initial stage of durability was -3.
2.98 mC / kg, the influence of environmental changes was small. The charge amount after 30,000-sheet running was -32.47 mC / kg, and even under high temperature and high humidity, the charge was not significantly reduced before and after running, and the image was good. Table 4 shows the results.

Example 2-9 A target toner was obtained in the same manner as in Example 2-1 except that dimethylethoxysilane was used as a coupling agent in an amount of 0.1 part by mass. When the particle size of the toner was measured by the above-described method, the number average particle size was 8.55 μm. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having granular irregularities of about 44 nm in diameter on the order of nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the particle surface of the toner determined by EPMA was 15.35.
% By mass. Similarly, the proportion of silicon atoms in the particle cross section of the toner was 0.02% by mass. Therefore, the abundance ratio of silicon atoms on the particle surfaces of the toner was 768 times the abundance ratio of silicon atoms on the cross section of the toner particles. Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the surface of the toner particles was 14.46% by mass. Therefore, the reduction rate of silicon atoms present on the toner particle surface before and after washing with the surfactant is 5.80%.
Met. Thus, it was confirmed that the coating layer formed on the particle surface of the toner obtained above was a layer in which the granular mass was fixed.

Subsequently, a two-component developer was prepared using the obtained toner in the same manner as in Example 2-1.
The charge amount of the toner of the component developer is 25 ° C. and the humidity is 30% R.
When measured under the environment of h, it was -32.54 mC / kg. Furthermore, using this developer, 25 ° C., humidity 30
In an environment of% Rh, an image is formed using a modified full-color laser copier copying machine CLC700 manufactured by Canon Inc.
A 30,000-sheet durability test was performed in the same manner as in Example 2-1. When the charge amount of the toner of the two-component developer after the durability test was measured, it was −31.10 mC / kg, and it was confirmed that a stable charge amount was maintained even during durability. The image after the durability test was satisfactory without any deterioration.

Further, the same measurement was conducted at 30 ° C. and 80% humidity.
When the test was performed in an environment of Rh, the charge amount in the initial stage of durability was -3.
0.89 mC / kg, the influence of environmental changes was small. The charge amount after 30,000-sheet running was −30.40 mC / kg, and even under high temperature and high humidity, the charge was not significantly reduced before and after running, and the image was good. Table 4 shows the results.

[Comparative Example 2-1] The same procedure as in Example 2-1 was carried out except that the black toner particles used as the base in Example 2-1 were used without forming a coating layer on the surface.
A two-component developer was prepared in the same manner as described above. Subsequently, using the obtained toner, a two-component developer was prepared in the same manner as in Example 2-1. The toner charge of the two-component developer was adjusted to 25 ° C. and a humidity of 30% Rh. It was -10.40 mC / kg when measured under the environment. Further, using this developer, an image was formed using a modified full color laser copier copying machine CLC700 manufactured by Canon in an environment of 25 ° C. and a humidity of 30% Rh, and the same 30,000 as in Example 2-1 was formed. A durability test was performed on the sheets. When the charge amount of the toner of the two-component developer after the durability test was measured, it was -8.95 mC.
/ Kg, and the charge amount after durability was slightly reduced.

Further, the same measurement was conducted at 30 ° C. and 80% humidity.
When the test was performed in an environment of Rh, the charge amount in the initial stage of durability was −
The value was 5.24 mC / kg, which was lower than the initial charge amount in an environment of 25 ° C. and a humidity of 30% Rh, and environmental fluctuation of the charge amount was observed. The charge amount after the end of 30,000 sheets is -3.3.
It was 2 mC / kg, and even under high temperature and high humidity, a decrease in withstand voltage due to durability was observed. Table 4 shows the results.

[Comparative Example 2-2] With respect to 100 parts by mass of black toner particles used as a base in Example 2-1.
5 parts by mass of hydrophobized silica fine powder having a weight average particle size of 40 nm was added and mixed with a Henschel mixer to obtain a toner in which silica fine powder was externally added as a fluidizing agent. When the particle size of this toner was measured by the method described above,
The weight average particle size was 8.33 μm. Observation of this toner with a scanning microscope photo revealed that although particles were observed on the surface of the toner particles, many gaps were present between the particles and the particles were not formed into a film. Furthermore,
The transmission electron micrograph of the cross section of the toner confirmed that particles were present in some places on the surface of the toner particles and a continuous layer was confirmed, but a continuous layer was not confirmed.

Further, the content of silicon atoms on the particle surface of the toner determined by EPMA was 0.45% by mass. Similarly, the abundance ratio of silicon atoms in the particle cross section of the toner was 0.00% by mass. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the abundance ratio of silicon atoms on the surface of the toner particles was 0.30% by mass. Therefore, the reduction rate of silicon atoms present on the surface of the toner particles before and after washing with the surfactant was 33.33%. Therefore, this toner was not recognized as a fixed layer because silicon was largely reduced by washing with a surfactant.

Subsequently, using the obtained toner, a two-component developer was prepared in the same manner as in Example 2-1.
The charge amount of the toner of the component developer is 25 ° C. and the humidity is 30% R.
When measured under the environment of h, it was -29.80 mC / kg. Furthermore, using this developer, 25 ° C., humidity 30
In an environment of% Rh, an image is formed using a modified full-color laser copier copying machine CLC700 manufactured by Canon Inc.
A 30,000-sheet durability test was performed in the same manner as in Example 2-1. When the charge amount of the toner of the two-component developer was measured after the durability test, it was -26.40 mC / kg, and it was confirmed that a stable charge amount was maintained even during durability. The charge amount after running was slightly reduced.

Further, the same measurement was conducted at 30 ° C. and 80% humidity.
When the test was performed in an environment of Rh, the charge amount in the initial stage of durability was -1.
The value was 9.45 mC / kg, which is lower than the initial charge amount in an environment of 25 ° C. and a humidity of 30% Rh, and environmental change of the charge amount was observed. . The charge amount after running 30,000 sheets is -1
It was 7.23 mC / kg, and similarly under high temperature and high humidity, a decrease in the withstand voltage due to durability was observed. Table 4 shows the results.

Table 3 summarizes the characteristics of the toner particles and the toner in Examples 2-1 to 2-9 and Comparative examples 2-1 and 2-2. Table 4 collectively shows the results of the image evaluation test when the developers using the toners in Examples 2-1 to 2-9 and Comparative Examples 2-1 and 2-2 were used.

[0248]

[Table 3]

[0249]

[Table 4]

[Example 3-1] <Preparation of parent toner particles> First, parent toner particles were prepared as follows.・ Methanol 95 parts by mass ・ Styrene 40 parts by mass ・ Polyvinylpyrrolidone 5 parts by mass ・ n-butyl acrylate 10 parts by mass ・ 2,2-azobisisobutyronitrile 2 parts by mass ・ Carbon black 2 parts by mass

After sufficiently stirring and dissolving and dispersing the above-mentioned materials, they were placed in a reaction vessel purged with nitrogen, heated to 65 ° C. under a nitrogen stream, and reacted for 20.0 hours. The resulting reaction was filtered, the filtrate was diluted with methanol, stirred thoroughly, and then filtered again. This operation of dilution and washing was repeated three times in total. Next, the obtained filtrate was sufficiently dried with a vacuum dryer to obtain black toner particles. The number average particle diameter of the obtained black toner particles was 5.04 μm, and the standard deviation was 0.61. Therefore, the variation coefficient of the number distribution of the black toner particles was 12.10%.

<Method of Forming Coating Layer Formed by Attachment of Granular Lumps Containing at Least Silicon Compound> 0.9 parts by mass of the base black toner particles obtained by the above-mentioned method were mixed with 40 parts by mass of methanol. Disperse in
Thereafter, 2.5 parts by mass of tetraethoxysilane was dissolved. Next, this solution was added to a 28% NH ₄ OH aqueous solution 1
It was added dropwise to a mixed solution in which 100 parts by mass of methanol was added to 0 parts by mass, and the mixture was stirred at room temperature for 48 hours to deposit a condensate film of a silicon compound on the surface of the toner particles. After completion of the reaction, the obtained particles are washed with purified water and then methanol, and then the particles are separated by filtration and dried to form a coating layer formed by fixing at least the granular lumps containing the silicon compound. A coated black toner of this example was obtained.

When the particle size distribution of the obtained toner was measured, the number average particle diameter was 5.45 μm, the standard deviation was 1.09, and the coefficient of variation of the number distribution was 20.00.
%, Which is a toner having a small particle size and a sharp particle size distribution. Observation of the particle surface of this toner with a scanning electron microscope photograph revealed that the particle surface of the toner was approximately 40 nm.
A coating layer having fine granular irregularities with a fine diameter was observed. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, according to EPMA, the ratio of silicon atoms present on the toner surface determined by the above-mentioned method was 10.
It was 70% by mass. The silicon atom abundance ratio in the toner cross section determined in the same manner was 0.03% by mass.
Therefore, the ratio of silicon atoms on the toner surface to silicon atoms on the toner cross section was 319.05, and it was found that polycondensates of the silicon compound hardly existed inside the toner particles. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surface of the toner was 8.54% by mass.
Therefore, the rate of change of silica present on the surface of the toner particles before and after washing with the surfactant was 20.14%. Therefore, it was confirmed that a coating layer formed by fixing the granular lumps to each other was formed on this toner.

A two-component developer was prepared by mixing 5 parts by weight of the toner obtained as described above and 95 parts by weight of a carrier obtained by coating a ferrite core having a particle diameter of 40 μm with a silicone resin. When the charge amount of the two-component developer was measured in the same manner as in Example 1-1, it was -46.36 m.
C / kg.

[Evaluation] Each of the two-component developers obtained above was evaluated for fixability, dot reproducibility and durability in the following manner. (Fixability) Copy a solid image on an OHP sheet,
A part of the obtained image was cut out, the image was observed at a magnification of 1000 using a scanning electron microscope, and the fixing property was evaluated based on whether or not the toner particle shape remained. As a result, no toner particle shape was observed on the observed image.

(Dot Reproducibility) A full-color laser copier copying machine C manufactured by Canon in an environment of 25 ° C. and a humidity of 30%.
LC700, process speed 200mm / sec,
Transfer current of 40 μA under 25 ° C./30% Rh environment
, And as an exposure light source, a wavelength of 68
The original image was copied using a modified machine modified to use a semiconductor laser having an output of 35 mW at 0 nm. Then, the toner image on the drum before transfer to the transfer paper was observed under a microscope, and the dot reproducibility was evaluated. As a result, the dot shape of the toner image was reproduced uniformly over the entire image, there was no fogging or scattering, and the dot reproducibility was excellent.

(Durability) Subsequently, the same apparatus as that used in the above-described dot reproducibility test was used at 25 ° C. and 30% humidity.
100,000 images were produced under the environment described above. After the endurance, the charge amount of the toner and the toner image formed on the drum were observed to evaluate the dot reproducibility. As a result, the charge amount was -43.26 mC / kg, and the charge amount tended to be slightly lower than before the endurance, but the degree of reduction was such that there was no practical problem. When the dots on the drum were evaluated after the image formation on the 100,000th sheet, the scattering was slightly increased as compared with the initial stage of the endurance, but an image having a uniform dot shape and excellent dot reproducibility was obtained.

[Example 3-2] The same black toner particles as used in Example 3-1 were used as a base, and tetrametal, a constituent of the condensate film of the metal compound used in Example 3-1 was used. 2.5 parts by weight of ethoxysilane, 2.0 parts by weight of tetraethoxysilane, 0.1 part by weight of methyltriethoxysilane.
A black toner of this example was prepared in the same manner as in Example 3-1 except that the amount was changed to 5 parts by mass. The number average particle diameter of the obtained toner is 5.31 μm, and the standard deviation is 0.6.
The coefficient of variation of the number distribution was 11.86%. When the particle surface of the obtained toner was observed with a scanning electron microscope photograph, a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA according to the method described above was 4.21% by mass. The silicon atom abundance ratio in the toner cross section similarly determined was 0.06% by mass. Therefore, the ratio of silicon atoms on the toner surface to silicon atoms on the cross section of the toner was 74.69, and almost no polycondensate of the silicon compound was present inside the toner particles.

Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 3.20% by mass. Accordingly, the rate of change of silica present on the surface of the toner particles before and after washing with the surfactant was 24.15%. Therefore, it was confirmed that a coating layer formed by fixing the granular lumps was formed on the particle surface of the toner. Using the black toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. I got

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured in the same manner as in Example 3-1, it was -47.96 mC / kg.

(Fixability) A solid image was copied on an OHP sheet, a part of the obtained image was cut out, and the image was observed at a magnification of 1000 using a scanning microscope. The fixability was evaluated based on whether or not it was.
As a result, no toner particle shape was observed on the observed image.

(Dot Reproducibility) The dot shape of the toner image formed on the drum was uniform, without fogging or scattering, and showed high dot reproducibility.

(Durability) The charge amount after the durability test was -46.69.
mC / kg, and the charge amount was slightly reduced. 10
When the dots on the drum were evaluated after the formation of the image on the tenth sheet, dot reproducibility equivalent to that at the beginning of the endurance was shown.

Example 3-3 0.02 parts by mass of polyvinyl alcohol was mixed with ethanol / water = 1: 1 mixed solution 2
0.0 parts by mass, and 0.9 parts by mass of the same black toner particles as those used as a base in Example 3-1 were dispersed therein, and then 3- (methacryloxypropyl) trimethoxysilane was dispersed therein. 5 parts by weight were dissolved. Thereafter, 120.0 parts by mass of water was gradually added dropwise, and after the addition was completed,
By stirring for 5 hours, the alkoxysilane was swollen into the black toner particles. Then, in the system,
A sol-gel reaction was performed by adding 20.0 parts by mass of a 28% NH ₄ OH solution and stirring at room temperature for 12 hours.
After the completion of the reaction, the obtained black toner was washed with ethanol to wash the unreacted silicon compound inside the particles, separated by filtration, and then dried to obtain the black toner of this example.

The obtained toner has a number average particle size of 5.43.
μm, the standard deviation was 0.77, and the coefficient of variation of the number distribution was 14.48%. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA by the above method was 5.82% by mass. The proportion of silicon atoms in the cross section of the toner determined by the same method was 0.44% by mass. Therefore, the ratio of silicon atoms on the toner surface to the abundance of silicon atoms on the toner cross section is 13.13, and the coating layer formed by fixing at least the granular lumps containing the silicon compound is formed on the toner surface. It was confirmed that it was done.

Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surface of the toner was measured and found to be 4.53% by mass. Accordingly, the rate of change of silica present on the surface of the toner particles before and after the surfactant was washed was 22.12.
%Met. Therefore, it was confirmed that a coating layer formed by fixing the granular lumps was formed on the particle surface of the toner. Using the black toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. I got

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured by the same method as in Example 3-1, it was -45.86 mC / kg.

(Fixing Property) A solid image was copied on an OHP sheet, a part of the obtained image was cut out, and the image was observed at a magnification of 1000 using a scanning microscope. The fixability was evaluated based on whether or not it was.
As a result, although the particle shape was partially observed, the surface was entirely smooth.

(Dot Reproducibility) The dot shape was uniform, there was no fogging or scattering, and sufficient dot reproducibility was exhibited.

(Durability) The charge amount after the durability test was -44.48.
mC / kg, and the charge amount was slightly reduced. 10
When the toner image on the drum after 10,000 sheets was evaluated, dot reproducibility equivalent to that before endurance was shown.

Example 3-4 Dibutyl phthalate (4 parts by mass) was finely dispersed in a 0.3 mass% aqueous solution of sodium dodecyl sulfonate (120.0 parts by mass) using an ultrasonic homogenizer to prepare a dibutyl phthalate emulsion. . Next, 0.9 parts by mass of the black toner particles used as the base in Example 3-1 were dispersed in 4.0 parts by mass of 0.3% by mass of sodium dodecyl sulfonate to prepare a toner particle dispersion. Thereafter, the dibutyl phthalate dispersion and the toner particle dispersion were mixed and stirred at room temperature for 2 hours. Next, a dispersion obtained by finely dispersing 3- (methacryloxypropyl) trimethoxysilane in a 0.3% by mass aqueous solution of sodium dodecylsulfonate using an ultrasonic homogenizer is charged into the toner dispersion, and stirred at room temperature for 4 hours. Was. Thereafter, 10 parts by mass of a 30% by mass aqueous NH ₄ OH solution was added thereto, and the mixture was stirred at room temperature for 12 hours to perform a sol-gel reaction. After completion of the reaction, a large amount of ethanol was charged into the system to remove unreacted 3- (methacryloxypropyl) trimethoxysilane and dibutyl phthalate inside the particles. Next, the obtained toner was washed again with ethanol, washed with purified water, filtered and dried to obtain a black toner.

When the particle size of the obtained toner was measured,
The number average particle diameter is 5.21 μm and the standard deviation is 0.5
The coefficient of variation of the number distribution was 10.36%. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA according to the method described above was 6.23% by mass. The silicon atom abundance ratio in the toner cross section similarly determined was 0.30% by mass. Therefore, the ratio of silicon atoms on the toner surface to silicon atoms on the toner cross section is 20.75, and the coating layer formed by fixing at least the granular lumps containing the silicon compound is formed on the toner surface. Was confirmed. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 5.58%. Accordingly, the rate of change of silica present on the surface of the toner particles before and after the surfactant is washed is 10.
46%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together. Using the black toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. I got

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1.

(Initial Charge Amount) The charge amount was measured by the same method as in Example 3-1 to be -47.55 mC / kg.

(Fixing Property) A solid image was copied on an OHP sheet, a part of the obtained image was cut out, and observed with a scanning microscope at 1000 × to determine whether the toner particle shape remained. Was evaluated. As a result, although the particle shape was partially observed, the surface was entirely smooth.

(Dot Reproducibility) The dot shape was uniform, there was no fogging, and the dot reproducibility was excellent.

(Durability) The charge amount after the durability test was -46.87.
mC / kg, and the charge amount was slightly reduced. 1
When the toner image on the drum after 100,000 sheets was evaluated, dot reproducibility equivalent to that before endurance was shown.

Example 3-5 A solution obtained by mixing 2 parts by mass of isopentyl acetate and 4 parts by mass of 3- (methacryloxypropyl) trimethoxysilane was added to 30 parts by mass of a 0.3% by mass aqueous solution of sodium dodecylsulfonate. After doing
Using an ultrasonic homogenizer, a dispersion of isopentyl acetate and methyltriethoxysilane was prepared. Next, 0.1% of the black toner particles used as a base in Example 3-1.
9 parts by mass were dispersed in 30 parts by mass of a 0.3% by mass aqueous solution of sodium dodecyl sulfonate, and the above-mentioned isopentyl acetate and methyltriethoxysilane dispersion were added thereto.
Stirred for hours. Then, a 28 mass% NH ₄ OH aqueous solution 5
The sol-gel reaction was carried out by mixing parts by mass and stirring at room temperature for 12 hours. Next, a large amount of ethanol was charged into the system to remove unreacted methyltriethoxysilane and isopentyl acetate from the inside of the toner particles. After the particles were washed again with ethanol, the particles were washed with purified water, filtered and dried to obtain a black toner.

When the particle size of the obtained toner was measured,
The number average particle diameter is 5.20 μm, and the standard deviation is 0.6.
The coefficient of variation of the number distribution was 13.27%. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA according to the method described above was 5.99% by mass. The silicon atom abundance ratio in the cross section of the toner similarly determined was 0.39% by mass. Therefore, the ratio of the silicon atoms on the toner surface to the silicon atoms on the toner cross section is 15.36, and the coating layer formed by fixing at least the granular lumps containing the silicon compound is formed on the toner surface. Was confirmed.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 4.30%. Therefore, the rate of change of the silica present on the toner particle surface before and after the surfactant was washed was 28.22%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together. Using the black toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. I got

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured in the same manner as in Example 3-1, it was -47.59 mC / kg.

(Fixing Property) A solid image was copied on an OHP sheet, a part of the obtained image was cut out, and observed with a scanning microscope at 1000 times to determine whether the toner particle shape remained. Was evaluated. As a result, although the particle shape was partially observed, the surface was entirely smooth.

(Dot Reproducibility) The dot shape was uniform, there was no fogging, and the dot reproducibility was excellent.

(Durability) The charge amount after durability was -45.69.
mC / kg, and the charge amount was slightly reduced. 10
When the toner image on the drum after 10,000 sheets was evaluated, dot reproducibility equivalent to that before durability was shown.

Example 3-6 A similar method was used except that 5 parts by mass of 3- (methacryloxypropyl) trimethoxysilane was dissolved in the reaction system in preparing the toner of Example 3-1. After the polymerization was carried out, the system was made alkaline by adding an aqueous NH ₄ OH solution, and then washed with a large amount of ethanol to remove unreacted 3- (methacryloxypropyl) trimethoxysilane inside the particles. Next, the mixture was filtered and dried to obtain a black toner.

When the particle size of the obtained toner was measured,
The number average particle diameter is 5.68 μm, and the standard deviation is 0.9.
It was 8 μm, and the coefficient of variation of the number distribution was 17.25%. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA by the above method was 4.42% by mass. The silicon atom abundance ratio in the cross section of the toner similarly determined was 0.12% by mass. Therefore, the ratio of the silicon atoms on the toner surface to the silicon atoms on the toner cross section is 37.94, and the coating layer formed by fixing at least the granular lumps containing the silicon compound is formed on the toner surface. Was confirmed.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 3.38% by mass. Therefore,
The rate of change of silica present on the toner particle surface before and after washing with the surfactant was 23.56%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together. Using the black toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. I got

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1.

(Initial charge amount) The charge amount was measured by the same method as in Example 3-1 and was -47.59 mC / kg.

(Fixing Property) A solid image was copied on an OHP sheet, a part of the obtained image was cut out, and observed with a scanning microscope at 1000 × to determine whether the toner particle shape remained. Was evaluated. As a result, no particle shape was observed.

(Dot Reproducibility) The shape of the dots is uniform.
There was no fogging and the dot reproducibility was excellent.

(Durability) The charge amount after durability was -46.32.
mC / kg, and the charge amount was slightly reduced. 1
When the toner image on the drum after 100,000 sheets was evaluated, dot reproducibility equivalent to that before durability was shown.

[Example 3-7] In the method of producing a toner performed in Example 3-3, the washing performed after the sol-gel reaction for forming the coating layer was performed only with water, so that the unreacted portion inside the particles was obtained. Except that the alkoxide was kept inside the particles, it was dispersed again in water and heated to 50 ° C., except that the sol-gel reaction was allowed to proceed to the inside of the particles. A black toner having a coating layer formed by fixing the granular masses containing the toner particles was prepared.

As for the particle size of the obtained toner, the number average particle size is 6.89 μm, the standard deviation is 1.05 μm,
The coefficient of variation of the number distribution was 15.24%. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA according to the method described above was 6.32% by mass. The silicon atom abundance ratio in the toner cross section similarly determined was 5.45% by mass. Therefore, the ratio of silicon atoms on the toner surface to the ratio of silicon atoms on the toner cross section was 1.16, indicating that the polycondensate of the silicon compound was present relatively inside the toner.

Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 4.99% by mass. Therefore,
The rate of change of silica present on the particle surface of the toner before and after washing with the surfactant was 21.11%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together. Using the black toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. I got

[Evaluation] The toner and the two-component developer obtained as described above were evaluated in the same manner as in Example 3-1.

(Initial charge amount) The charge amount was measured by the same method as in Example 3-1 to be -47.55 mC / kg.

(Fixing Property) Although the particle shape was slightly large, it was barely a problem.

(Dot Reproducibility) The dot shape was uniform, there was no fogging, and the dot reproducibility was excellent.

(Durability) The charge amount after the durability test was -46.98.
mC / kg, and the charge amount was slightly reduced. 1
When the toner image on the drum after 100,000 sheets was evaluated, dot reproducibility equivalent to that before durability was shown.

[Example 3-8] Black was prepared in the same manner as in Example 3-2 except that the amounts of tetraethoxysilane and methyltriethoxysilane were changed to 10.0 parts by mass and 5 parts by mass, respectively. A toner was obtained. The number average particle diameter of the obtained particles is 6.55 μm, and the standard deviation is 0.5.
85, and the coefficient of variation of the number distribution was 12.98%. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content of silicon atoms on the toner surface determined by EPMA according to the above-mentioned method was 20.16% by mass.
Met. The proportion of silicon atoms in the cross section of the toner similarly determined was 0.19% by mass. Therefore, the ratio of silicon atoms on the toner surface to the ratio of silicon atoms on the toner cross section is 107.91, and the coating layer formed by fixing the granular lumps containing at least the silicon compound is formed on the toner surface. It was confirmed that. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 16.09% by mass. Therefore, the rate of change of silica present on the particle surface of the toner before and after washing with the surfactant was 20.21%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together. Using the black toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. I got

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured by the same method as in Example 3-1, it was -45.23 mC / kg.

(Fixing property) Although many particle shapes were observed,
It was barely a problem.

(Dot Reproducibility) The dot shape was uniform, there was no fogging and scattering, and the dot reproducibility was excellent.

(Durability) The charge amount after the durability test was -45.24.
mC / kg, and the charge amount was slightly reduced. 1
When the toner image on the drum after 100,000 sheets was evaluated, dot reproducibility equivalent to that before durability was shown.

[Example 3-9] The amounts of tetraethoxysilane and methyltriethoxysilane used in the toner production method of Example 3-2 were respectively 0.9 parts by mass of tetraethoxysilane and methyltriethoxysilane. A black toner was prepared in the same manner except that the amount was changed to 0.3 parts by mass. The obtained toner had a number average particle diameter of 5.33 μm, a standard deviation of 0.99, and a coefficient of variation in number distribution of 18.57%. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA according to the method described above was 1.01% by mass. The silicon atom abundance ratio in the cross section of the toner similarly determined was 0.01% by mass. Accordingly, the ratio of silicon atoms on the toner surface to the ratio of silicon atoms on the toner cross section is 92.14, and the coating layer formed by fixing the granular lumps containing at least the silicon compound is formed on the toner surface. It was confirmed that.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 0.92% by mass. Accordingly, the rate of change of silica present on the surface of the toner particles before and after washing with the surfactant was 9.24%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together. Using the black toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. I got

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured in the same manner as in Example 3-1, it was -40.21 mC / kg.

(Fixing property) The particle shape was not confirmed, and the fixing property was good.

(Dot Reproducibility) The dot shape was uniform, there was no fogging and scattering, and the dot reproducibility was excellent.

(Durability) The charge amount after durability was -36.02.
mC / kg, and the charge amount was slightly reduced. 1
When the toner image on the drum after 100,000 sheets was evaluated, fogging and scattering slightly increased from before the endurance, but the dot shape was uniform and the dot reproducibility was good.

[Example 3-10] In the toner production method performed in Example 3-1, after the polymerization was completed, the reaction system was cooled to room temperature, and then 20 parts by mass of methanol was added to 20 parts by mass of the reaction solution. 28 parts by mass of tetraethoxysilane and 7 parts by mass of methyltriethoxysilane were dissolved in the solution thus obtained, and this solution was added to a 28% NH ₄ OH solution
The solution was added dropwise to a solution in which 100 parts by mass of methanol was added to 100 parts by mass, and stirred at room temperature for 48 hours to deposit a condensate film of a silicon compound on the toner particles. After the reaction, the obtained particles are washed with purified water and then methanol, and then filtered and dried, whereby the particles are coated with a coating layer formed by fixing at least the granular lumps containing the silicon compound. Toner was obtained.

The number average particle diameter of the obtained particles was 5.29 μm.
m, the standard deviation was 0.71, and the coefficient of variation of the number distribution was 13.42%. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA by the above method was 4.15% by mass. The silicon atom abundance ratio in the cross section of the toner similarly determined was 0.05% by mass. Therefore, the ratio of the silicon atoms on the toner surface to the silicon atoms on the toner cross section is 83.00, and the coating layer formed by fixing at least the granular lumps containing the silicon compound is formed on the toner surface. Was confirmed.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 3.23% by mass. Therefore,
The rate of change of silica present on the surface of the toner particles before and after washing with the surfactant was 22.14%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together. Using this toner as a one-component developer, the toner was charged into a commercialized electrophotographic copying machine FC-2 (manufactured by Canon Inc.) and its temperature was changed to 25.
The same evaluation as in Example 3-1 was performed in an environment of 30 ° C. and a humidity of 30% Rh, and the following results were obtained.

[Evaluation] The single-component developer obtained above was evaluated in the same manner as in Example 3-1. (Initial charge amount) The charge amount was measured by the same method as in Example 3-1 and was -47.89 µq /.

(Fixing property) A solid image was copied on an OHP sheet, a part of the obtained image was cut out, and observed with a scanning microscope at 1000 times to determine whether the toner particle shape remained. Was evaluated. As a result, no particle shape was observed.

(Dot Reproducibility) The dot shape was uniform, and the dot reproducibility was excellent without fogging and scattering.

(Durability) The charge amount after durability was -45.14.
mC / kg, and the charge amount was slightly reduced. 1
Evaluation of the image after 100,000 sheets showed dot reproducibility equivalent to that before endurance.

Example 3-11 A black toner was prepared in the same manner as in Example 3-2 except that toner particles serving as a base were prepared in the following manner. <Preparation of Toner Particles as Base> To a reaction vessel equipped with a high-speed stirrer TK-homomixer, 890 parts by mass of ion-exchanged water and 95 parts by mass of polyvinyl alcohol were added, and the number of revolutions was adjusted to 3600 rpm. It was heated. 85 parts by mass of styrene monomer 34 parts by mass of n-butyl acrylate monomer 10 parts by mass of carbon black After dispersing the above mixture for 3 hours using an attritor,
3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile), which is a polymerization initiator, was added, and this dispersion was charged into the above-mentioned dispersion medium. Granulation was performed for 10 minutes while maintaining the rotation speed. Then, at 50 rpm, 55 ° C for 1 hour, 65
The polymerization was carried out at 4 ° C. for 4 hours and further at 80 ° C. for 5 hours.

After the completion of the polymerization, the slurry was cooled and the dispersant was removed by repeating washing with purified water. Further washing,
By drying, black toner particles serving as a base were obtained. By repeating the classification, the toner particles obtained by the above method have a number average particle diameter of 10.24 μm, a standard deviation of 1.20, and a coefficient of variation of the number distribution of 11.71%.
As toner particles. Using the toner particles as a base, the toner particles were treated in the same manner as in Example 3-2.
A coating layer formed by fixing at least the granular masses containing a silicon compound was provided, and a black toner was prepared.

The obtained toner has a number average particle diameter of 1
0.60 μm, the standard deviation was 1.38, the coefficient of variation in the number distribution was 13.03%, and the toner had a relatively large particle size. Observation of the particle surface of this toner with a scanning microscope photograph revealed that about 4
A coating layer having fine granular irregularities with a diameter of 0 nm was observed. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Further, the content of silicon atoms on the toner surface determined by EPMA by the above method was 13.05% by mass.
Met. The silicon atom abundance ratio in the toner cross section similarly determined was 0.04% by mass. Therefore, the ratio of silicon atoms on the toner surface to silicon atoms on the toner cross section was 326.25. Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 10.38%. Accordingly, the rate of change of silica present on the surface of the toner particles before and after washing with the surfactant was 20.45%.
Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together.

Using the toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. Was obtained.

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured in the same manner as in Example 3-1, it was -42.14 mC / kg.

(Fixing property) No particles were observed, indicating good fixing property.

(Dot Reproducibility) Scattering and fogging slightly occurred, dots were connected in some places, and the shape was not uniform, but there was no problem in image quality.

(Durability) The charge amount after durability was -41.53.
mC / kg, and the charge amount was slightly reduced. 10
The toner image on the drum after 10,000 sheets was almost the same as before the endurance.

Example 3-12 A black toner was produced in the same manner as in Example 3-3 except that the classification conditions of the toner particles used as the base were changed. The number average particle diameter of the obtained toner is 6.59 μm, and the standard deviation is 1.8.
9, and the coefficient of variation of the number distribution was 28.68%. Example 3 was performed using the toner obtained by the above method.
A two-component developer was prepared in the same manner as in Example 1, and Example 3-
Evaluation was performed in the same manner as in Example 1, and the following results were obtained.

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured in the same manner as in Example 3-1, it was -42.01 mC / kg.

(Fixing property) No particle shape was observed, indicating good fixing property.

(Dot Reproducibility) Scattering between dots and fogging slightly occurred, and the dot shape was not uniform.
Although the image quality was slightly inferior, there was virtually no problem.

(Durability) The charge amount after durability was -41.25.
mC / kg, and the charge amount was slightly reduced. 1
The toner image on the drum after 100,000 sheets was the same as before the endurance.

[Comparative Example 3-1] The coated black toner particles used as the base material in Example 3-1 were not provided with a coating layer formed by fixing at least the granular lumps containing the silicon compound. Example 3-1
A two-component developer was prepared in the same manner as described above. This developer was evaluated in the same manner as in Example 3-1.

[Evaluation] The two-component developer obtained above was evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured in the same manner as in Example 3-1, it was -7.56 mC / kg.

(Fixing Property) A solid image was copied on an OHP sheet, a part of the obtained image was cut out, and observed with a scanning microscope at 1000 × to determine whether the toner particle shape remained. Was evaluated. As a result, no particle shape was observed.

(Dot Reproducibility) The image density was extremely low.
The dots had disappeared in some places, and the dots had not been sufficiently reproduced.

(Durability) When the durability test was performed on ten sheets, the toners fused to each other on the 3,000th sheet, and the durability could not be advanced.

[Comparative Example 3-2] In Example 3-6,
A black toner was obtained in the same manner except that tetraethoxysilane was substituted for 3- (methacryloxypropyl) trimethoxysilane and that no hydrolysis and polycondensation reaction of tetraethoxysilane was caused by not adding NH ₄ OH. . The number average particle diameter of the obtained toner was 5.10 μm, the standard deviation was 0.79, and the coefficient of variation of the number distribution was 15.49%.

When the particle surface of this toner was observed with a scanning microscope photograph, granular particles were found on the particle surface of the toner in some places, but the individual particles existed apart from each other. Had not become. The transmission electron micrograph of the cross section of the particles of the toner was observed in the same manner, and no coating layer was confirmed. This is probably because the alkali treatment was not performed, so that the hydrolysis reaction of the silicon compound did not proceed, and a sufficient polycondensate to form the coating layer was not formed.

Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA according to the method described above was 0.03% by mass. The silicon atom abundance ratio in the cross section of the toner similarly determined was 0.01% by mass. Therefore, the ratio of silicon atoms on the toner surface to the ratio of silicon atoms on the toner cross section was 3.00. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 0.02% by mass. Therefore, the rate of change of silica present on the surface of the toner particles before and after the surfactant was washed was 33.33%,
It was not determined that a sufficient coating layer was formed on this toner. Using the toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. Obtained.

[Evaluation] The toner and the two-component developer obtained above were evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured in the same manner as in Example 3-1, the charge amount was as low as -10.25 mC / kg.

(Fixing Property) A solid image was copied on an OHP sheet, a part of the obtained image was cut out, and observed with a scanning microscope at 1000 × to determine whether the toner particle shape remained. Was evaluated. As a result, no particle shape was observed.

(Dot Reproducibility) The image density was low overall and the dots had disappeared in some places.

(Durability) When an endurance test was performed on 100,000 sheets, the toner was fused in the developing device on the 5,000th sheet, making development difficult. This is presumably because the silicon compound coating layer was not formed in the toner of this example.

[Comparative Example 3-3] With 100 parts by mass of the black toner particles used as a base in Example 3-2, 5 parts by mass of hydrophobic silica particles having an average particle diameter of 40 nm were mixed.
By mixing with a Henschel mixer, silica fine particles were externally added to the toner particle surface to obtain a black toner. When the particle size of this toner was measured, the number average particle size was 5.04 μm, the standard deviation was 0.98 μm, and the coefficient of variation of the number distribution was 19.44%.

When the particle surface of this toner was observed with a scanning microscope photograph, it was confirmed that fine particles having a diameter of about 40 nm existed on the particle surface of the toner. Was not formed. Observation with a transmission electron microscope photograph of the cross section of the particles of the toner showed similar results. Further, the abundance ratio of silicon atoms on the toner surface determined by EPMA by the method described above was 0.54% by mass. The content ratio of silicon atoms in the cross section of the toner similarly determined was 0.00% by mass.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 0.38% by mass. Therefore,
The rate of change of silica present on the surface of the toner particles before and after washing with the surfactant was 30.18%. The rate of change of the silicon concentration due to this washing was larger than that of the coating layer formed by fixing at least the granular lumps containing the silicon compound. Using the toner obtained by the above method, a two-component developer was prepared in the same manner as in Example 3-1 and evaluated in the same manner as in Example 3-1. The following results were obtained. Obtained.

[Evaluation] Each of the toner and the two-component developer obtained above was evaluated in the same manner as in Example 3-1. (Initial charge amount) When the charge amount was measured by the same method as in Example 3-1, it was -44.12 mC / kg.

(Fixing property) No particles were observed.

(Dot Reproducibility) The dot shape was uniform and excellent in dot reproducibility without scattering.

(Durability) The charge amount after durability was -21.0 m.
C / kg, and the charge amount was reduced. When the toner image on the drum after 100,000 sheets was observed, many scatters occurred, and the dot shape was uneven, and spots where dots were connected in some places were found. Table 3 below shows Example 3 in Tables 5 and 6.
The characteristics of the toner particles and the toner in Comparative Examples 1 to 3-12 and Comparative Examples 3-1 and 3-2 are shown together, and Table 7 shows the evaluation results.

[0362]

[Table 5]

[0363]

[Table 6]

[0364]

[Table 7]

The fixability in Table 7 was determined by developing and fixing a solid image on an OHP sheet, and then observing whether or not the toner particle shape remained at a magnification of 1000 using a scanning microscope.
The results are shown by the following criteria. A: No particles are observed. B: There are several places where the particle shape is maintained. C: Most of the particles maintain the particle shape.

In Table 7, the dot reproducibility was 25 ° C., humidity 3
Under an environment of 0%, the original image was copied using a modified full-color laser copier copying machine CLC700 manufactured by Canon, and the toner image on the drum before transfer to the receiving paper and after 100,000 sheets of durability were observed under a microscope. The results were shown based on the following criteria.

Example 4-1 <Preparation of Base Toner Particles> First, base toner particles used in the present example were prepared as follows. In a four-necked flask equipped with a high-speed stirrer TK-homomixer, 820 parts by mass of ion-exchanged water and 97 parts by mass of polyvinyl alcohol were added, the rotation speed was adjusted to 1000 rpm, and the mixture was heated to 55 ° C. to disperse the dispersion medium. Prepared.

On the other hand, a monomer dispersion was prepared as follows. 60 parts by mass of styrene polymer 40 parts by mass of n-butyl acrylate monomer 10 parts by mass of carbon black 1 part by mass of metal salicylate compound 20 parts by mass of mold release agent (paraffin wax 155) After dispersing for 3 hours using a lighter, 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator is added, and this dispersion is poured into the dispersion medium prepared above. Then, granulation was performed for 10 minutes while maintaining the rotation speed. After that, 50r
pm, 1 hour at 55 ° C, 4 hours at 65 ° C,
The polymerization was carried out at a temperature of 5 ° C. for 5 hours.

After completion of the polymerization, the slurry was cooled and unreacted substances were removed by repeating washing with purified water. After further washing and drying, black toner particles were obtained. When the particle size of the toner particles was measured, the number average particle size of the black toner particles was 6.01 μm. Further, when the glass transition point (Tg) of the toner particles was measured, it was 27.86 ° C.

<Method for Forming Coating Layer (Sol-Gel Film)> 0.8 parts by mass of the black toner particles obtained by the above method and 2.5 parts by mass of tetraethoxysilane are dispersed and dissolved in 40 parts by mass of methanol. A toner dispersion was prepared. Thereafter, the previously prepared toner dispersion liquid is dropped into a solution obtained by adding 100 parts by weight of methanol to 8 parts by weight of a 28% NH ₄ OH aqueous solution, and after the dropping is completed, the mixture is stirred at room temperature for 48 hours. After the hydrolysis and polycondensation, a sol-gel film was deposited on the surface of the toner particles. After completion of the reaction, the obtained particles were washed with purified water and then with methanol, and then the particles were separated by filtration and dried to obtain a toner of this example coated with a sol-gel film.

The particle diameter of the obtained toner was measured in the same manner as in Example 1-1.
It was 35 μm. Observation of the particle surface of this toner with a scanning microscope photograph revealed that about 40
A coating layer having fine granular irregularities with a diameter of nm was observed. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the abundance ratio of silicon atoms is as follows:
6.39% by mass. Furthermore, when the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner obtained in the same manner was 100%, the abundance ratio of silicon atoms was 0.07% by mass. Therefore, the amount of silicon atoms present on the particle surface of the toner was 91.00 times the amount of silicon atoms present on the particle cross section of the toner. Therefore, it was found that most of the polycondensate of the silicon compound was present on the surface of the toner particles, and was hardly present inside the toner particles.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 4.76% by mass.
Accordingly, the reduction ratio of silica present on the toner particle surface before and after the surfactant was washed was 25.46%. Therefore, it was confirmed that a coating layer formed by fixing the granular lumps was formed on the surface of the toner particles of the toner.

The melting start temperature of the toner obtained as described above was measured using a flow tester.
3.95 ° C. Further, the glass transition point (Tg) of this toner was determined, and it was 35.71 ° C. Therefore, the difference between the melting start temperature of this toner and the glass transition point is 1
8.24 ° C.

<Evaluation> The toner of this example obtained above was evaluated for blocking resistance and fixability by the following methods. The evaluation results of the toners of the examples and the comparative examples are summarized in Table 9. (1) Blocking resistance 30 g of the above toner was placed in a 30 ml sample bottle, and
After leaving the bottle in a thermostat at 0 ° C. for 2 days, the bottle was tilted to observe the fluidity, thereby performing a blocking test. As a result, it was confirmed that the toner kept good fluidity and had good blocking resistance.

(2) Fixability 5 parts by mass of the toner obtained above and a carrier 9 obtained by coating a ferrite core having a particle diameter of 40 μm with a silicone resin.
5 parts by mass to prepare a two-component developer. A solid image was printed on an OHP sheet using a modified machine in which the developer was changed from CLC500 to the following conditions. The fixing conditions at this time are shown below. Roll pressure = 3.43 × 10 ⁻¹ MPa (3.5 kg /
cm ² ) Roll speed 70 mm / sec. Fixing temperature 100 ° C. Process speed 200 mm / sec Next, a part of the obtained image is cut out, observed at a magnification of 1000 using a scanning microscope, and the fixability is determined based on whether or not the shape of the toner particles remains. evaluated. The observation was performed by observing five visual fields that do not completely overlap each other. As a result, no particle shape was observed.

[Example 4-2] 0.02 parts by mass of polyvinyl alcohol was dissolved in 25 parts by mass of a mixed solution of ethanol / water = 1: 1, and the solution was used as a base in Example 4-1. 0.9 parts by mass of the same black toner particles as above were dispersed, and then 5 parts by mass of hexyltrimethoxysilane was dissolved. Thereafter, 120 parts by weight of water was gradually added dropwise, so that hexyltrimethoxysilane was absorbed by the black toner particles. After completion of the addition, the mixture was stirred for 5 hours. Next, a sol-gel reaction (hydrolysis and polycondensation) was performed by adding 20 parts by mass of a 28% NH ₄ OH solution to the system and stirring at room temperature for 12 hours. After the reaction,
The unreacted alkoxide in the toner was washed by washing the obtained black toner particles with ethanol to obtain a black toner of this example. The number average particle diameter of the obtained toner was measured by the same method as in Example 4-1 and found to be 6.78 μm.

When the surface of the particles of the toner was observed with a scanning microscope photograph, a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the surface of the particles of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the proportion of silicon atoms is 4.
It was 75% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner obtained in the same manner was 100%, the silicon atom abundance was 0.26% by mass. Therefore, the amount of silicon atoms present on the particle surface of the toner was 18.05 times the amount of silicon atoms present on the cross section of the toner particle. Therefore, it was found that the polycondensate of the silicon compound was present more on the surface of the toner particles than on the inside of the toner particles.

Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 3.59% by mass.
Therefore, the reduction ratio of silica existing on the surface of the toner particles before and after the surfactant was washed was 24.58%.
Therefore, it was confirmed that the toner had a coating layer formed by fixing the granular lumps together.

The melting start temperature of the toner obtained above was measured using the same method as in Example 4-1.
4.69 ° C. The glass transition point (Tg) of this toner was determined in the same manner as in Example 4-1.
55 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 30.14 ° C.

Further, the above toner was subjected to a blocking test in the same manner as in Example 4-1. As a result, the toner retained good fluidity and had good blocking resistance. Example 4 using the above toner
A two-component developer was prepared in the same manner as in Example 1, and an image for fixing property evaluation was prepared using the two-component developer in the same manner as in Example 4-1 to evaluate the fixing property. Was done. As a result, no particle shape was observed and the fixability was good (see Table 9).

Example 4-3 4 parts by weight of dibutyl phthalate was finely dispersed in 100 parts by weight of a 0.5% by weight aqueous solution of sodium dodecylsulfonate using an ultrasonic homogenizer, and a dibutyl phthalate emulsion (dispersion liquid) was obtained. Was prepared. Next, 0.9 parts by mass of the same black toner particles as used as the base in Example 4-1 were dispersed in 6.0 parts by mass of 0.5% by mass of sodium dodecylsulfonate to prepare a toner particle dispersion. . Thereafter, the dibutyl phthalate dispersion and the toner particle dispersion were mixed and stirred at room temperature for 2 hours to introduce dibutyl phthalate into the black toner particles.

Next, a dispersion liquid in which 5 parts by mass of (3-glycidoxypropyl) methyldimethoxysilane was finely dispersed in a 0.5% by mass aqueous solution of sodium dodecylsulfonate using an ultrasonic homogenizer was prepared as described above. The mixture was charged into the toner dispersion and stirred at room temperature for 5 hours, whereby (3-glycidoxypropyl) methyldimethoxysilane was absorbed by the black toner particles. Then 30
10 parts by mass of a ₄ % by mass aqueous solution of NH ₄ OH was added, and the mixture was stirred at room temperature for 12 hours to perform a sol-gel reaction on the surface of black toner particles.

After the completion of the reaction, a large amount of ethanol was charged into the system to remove unreacted (3-glycidoxypropyl) methyldimethoxysilane and dibutylphthalate inside the toner. Next, the obtained toner particles are washed again with ethanol, washed with purified water, separated by filtration, and dried,
A black toner of this example was obtained. The number average particle diameter of the obtained toner was measured in the same manner as in Example 4-1 and found to be 6.89 μm.

When the particle surface of this toner was observed with a scanning microscope photograph, a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA was 100%, the content ratio of silicon atoms was 5.15% by mass. Further, when the total amount of carbon atoms, oxygen atoms, and silicon atoms in the cross section of the toner particles similarly determined was 100%, the abundance ratio of silicon atoms was 0.19% by mass. Therefore, the abundance of silicon atoms on the particle surface of the toner was 27.85 times the abundance of silicon atoms on the cross section of the particle of the toner.
Therefore, it was found that the polycondensate of the silicon compound was present more on the surface of the toner particles than on the inside of the toner particles.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 4.61% by mass. Therefore, the reduction rate of silica present on the particle surface of the toner before and after the surfactant was washed was 10.56%. Therefore, it was confirmed that a coating layer formed by fixing the granular lumps was formed on the particle surface of the toner.

The melting start temperature of the toner obtained above was measured using the same method as in Example 4-1.
7.64 ° C. The glass transition point (Tg) of this toner was determined in the same manner as in Example 4-1.
08 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 24.56 ° C.

Further, when the above-described blocking test of the toner was performed in the same manner as in Example 4-1, the toner maintained good fluidity and had good blocking resistance. Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1. Using this two-component developer, a two-component developer was prepared in the same manner as in Example 4-1 to evaluate the fixing property. An image was formed and the fixability was evaluated. As a result, no particle shape was observed and the fixability was good (see Table 9).

[Example 4-4] Isopropyl acetate 2.3
A solution obtained by mixing 4 parts by mass of (3-glycidoxypropyl) methyldimethoxysilane with 50 parts by mass of a 0.5% by mass aqueous solution of sodium dodecylsulfonate was added. After processing at 5000 rpm for 30 minutes with a K homomixer, using a Nanomizer system LA-30C manufactured by Cosmo Keiso Co., Ltd., a processing pressure of 1300 kg / c.
m ² , isopropyl acetate and (3-
A glycidoxypropyl) methyldimethoxysilane dispersion was prepared.

Next, 0.9 parts by mass of the same black toner particles as used as the base in Example 4-1 were dispersed in 40 parts by mass of a 0.5% by mass aqueous solution of sodium dodecylsulfonate. The prepared isopropyl acetate and (3-glycidoxypropyl) methyldimethoxysilane dispersion were added, and the mixture was stirred at room temperature for 2 hours. Next, 8 parts by mass of a 28% by mass aqueous NH ₄ OH solution was added and mixed, and the mixture was stirred at room temperature for 12 hours to perform a sol-gel reaction. Then, put a large amount of ethanol into the system,
Unreacted (3-glycidoxypropyl) methyldimethoxysilane and isopropyl acetate were removed from the inside of the toner particles. Further, the toner was washed again with ethanol, washed with purified water, separated by filtration, and dried to obtain a black toner of this example. The number average particle diameter of the obtained toner was measured in the same manner as in Example 4-1.
It was 6.57 μm.

When the particle surface of this toner was observed with a scanning microscope photograph, a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

Assuming that the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the abundance ratio of silicon atoms is 3.
It was 91% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner similarly determined was 100%, the abundance ratio of silicon atoms was 0.13% by mass. Therefore, the amount of silicon atoms present on the particle surface of the toner was 29.26 times the amount of silicon atoms present on the cross section of the particle of the toner. Therefore, it was found that the polycondensate of the silicon compound was present more on the surface of the toner particles than on the inside of the toner particles. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 3.12% by mass. Therefore, the reduction ratio of silica existing on the surface of the toner particles before and after the surfactant was washed was 20.14%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together.

The melting start temperature of the toner obtained above was measured using the same method as in Example 4-1.
6.24 ° C. The glass transition point (Tg) of this toner was determined in the same manner as in Example 4-1.
60 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 22.64 ° C.

Further, when the above-described blocking test of the toner was performed in the same manner as in Example 4-1, the toner maintained good fluidity and had good blocking resistance. Example 4-1 was prepared using the toner described above.
A two-component developer was prepared in the same manner as in Example 1, and an image for evaluating fixability was formed using this developer in the same manner as in Example 4-1 to evaluate the fixability. As a result, no particle shape was observed and the fixability was good (see Table 9).

[Example 4-5] The formulation amount of tetraethoxysilane used in the toner production method of Example 4-1 was changed to 5.
A sol-gel film-coated toner was obtained in the same manner as in Example 4-1 except that the amount was changed to 0 parts by mass. The number average particle diameter of the obtained toner was measured in the same manner as in Example 4-1 and found to be 6.59 μm.

When the particle surface of this toner was observed with a scanning microscope photograph, a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner. When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA was 100%, the abundance ratio of silicon atoms was 19.73% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner determined similarly was 100%, the abundance ratio of silicon atoms was 0.02% by mass. Therefore, the amount of silicon atoms present on the particle surface of the toner was 873.66 times the amount of silicon atoms present on the particle cross section.
Therefore, it was found that most of the polycondensate of the silicon compound was present on the surface of the toner particles, and was hardly present inside the toner particles.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 15.87% by mass.
Accordingly, the reduction rate of silica present on the surface of the toner particles before and after the surfactant was washed was 19.56%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together.

The melting start temperature of the toner obtained above was measured by the same method as in Example 4-1.
7.72 ° C. The glass transition point (Tg) of this toner was determined in the same manner as in Example 4-1.
48 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 34.24 ° C.

Further, when the above-mentioned blocking test of the toner was conducted in the same manner as in Example 4-1, the toner maintained good fluidity and had good blocking resistance. Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1. Using this developer, an image for fixing property evaluation was prepared in the same manner as in Example 4-1. , Fixability was evaluated. As a result, an average of 5.5 particles were observed in one visual field, but most of the particles were well fixed (see Table 9).

[Example 4-6] Except that 2 parts by mass of trimethoxysilane was further used in addition to 5 parts by mass of tetraethoxysilane used in forming the sol-gel film in the method for producing a toner of Example 4-5. A black toner of this example covered with a sol-gel film was obtained in the same manner as in Example 4-5. The number average particle diameter of the obtained particles was measured in the same manner as in Example 4-1 and found to be 6.82 μm. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the toner particle surface determined by EPMA is 100%, the abundance ratio of silicon atoms is 1
It was 2.79% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner obtained in the same manner was assumed to be 100%, the abundance ratio of silicon atoms was 0.06% by mass. Therefore, the abundance of silicon atoms on the particle surface of the toner was 221.65 times the abundance of silicon atoms on the cross section of the toner particle. Therefore, it was found that most of the polycondensate of the silicon compound was present on the surface of the toner particles, and was hardly present inside the toner particles. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surface of the toner was 9.71% by mass.
Met. Therefore, the reduction ratio of silica present on the surface of the toner particles before and after the surfactant was washed was 24.10%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together.

The melting start temperature of the toner obtained as described above was measured using the same method as in Example 4-1 and found to be 71.41 ° C. The glass transition point (Tg) of this toner was found to be 33.52 ° C. in the same manner as in Example 4-1. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 37.89 ° C.

Further, when the above-described blocking test of the toner was carried out in the same manner as in Example 4-1, the toner maintained good fluidity and had good blocking resistance. Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1. Using this developer, an image for fixing property evaluation was prepared in the same manner as in Example 4-1. , Fixability was evaluated. As a result, an average of 6.3 particle shapes were observed in one visual field, but most of the particles were well fixed (see Table 9).

[Example 4-7] In preparing the toner of Example 4-1, 5 parts by mass of (3-glycidoxypropyl) methyldimethoxysilane was added to the monomer dispersion, and The polymerization was carried out in the same manner as in Example 4-1 except that an aqueous NH ₄ OH solution was added to the mixture to make it alkaline. Thereafter, unreacted (3-glycidoxypropyl) methyldimethoxysilane in the inside of the particles is removed by washing with a large amount of ethanol, and then filtered and dried to obtain the black toner of this example. Was. The number average particle diameter of the toner obtained above was measured in the same manner as in Example 4-1 and found to be 6.22 μm.

When the particle surface of this toner was observed with a scanning microscope photograph, it was found that the surface of the
A coating layer having fine granular irregularities with a fine diameter was observed. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the proportion of silicon atoms is 4.
It was 10% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner similarly determined was 100%, the abundance ratio of silicon atoms was 4.00% by mass. Therefore, the abundance of silicon atoms on the particle surface of the toner was 1.03 times the abundance of silicon atoms on the particle cross section of the toner. Therefore,
It was found that the polycondensate of the silicon compound was present not only on the surface of the toner particles but also inside the toner particles at a similar ratio. Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 3.68% by mass. Therefore, the reduction ratio of silica present on the surface of the toner particles before and after the surfactant was washed was 10.25.
Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together.

The melting start temperature of the toner obtained above was measured using the same method as in Example 4-1.
2.99 ° C. The glass transition point (Tg) of this toner was determined in the same manner as in Example 4-1.
45 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 36.54 ° C.

Further, when the above-described blocking test of the toner was performed in the same manner as in Example 4-1, the toner retained good fluidity and had good blocking resistance. Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1. Using this developer, an image for fixing property evaluation was prepared in the same manner as in Example 4-1. , Fixability was evaluated. As a result, an average of 2.4 particles were observed in one visual field, but most of the particles were well fixed (see Table 9).

Example 4-8 Example 4-4 was repeated except that an ester wax (melting point: 50 ° C.) was added to the polymer composition in the method for producing base toner particles of Example 4-1.
In the same manner as in -1, toner particles were prepared. The number average particle diameter of the toner particles was measured in the same manner as in Example 4-1 and found to be 6.31 μm. Further, the glass transition point of the toner particles was 20.13 ° C.

[0412] The toner particles serving as the base obtained above were coated with a sol-gel film in the same manner as in Example 4-1 to prepare a toner of this example. The number average particle diameter of the obtained toner was measured in the same manner as in Example 4-1 and found to be 6.62 μm. Observation of the particle surface of the toner with a scanning microscope photograph revealed that a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the proportion of silicon atoms is 5.
It was 78% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner obtained in the same manner was assumed to be 100%, the abundance ratio of silicon atoms was 0.06% by mass. Therefore, the abundance of silicon atoms on the particle surface of the toner was 101.29 of the abundance of silicon atoms on the cross section of the particle of the toner. Therefore, it was found that most of the polycondensate of the silicon compound was present on the surface of the toner particles, and was hardly present inside the toner particles.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 4.88% by mass. Therefore, the reduction ratio of silica present on the toner particle surface before and after the surfactant was washed was 15.49%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together.

The melting start temperature of the toner obtained above was measured using the same method as in Example 4-1.
4.11 ° C. The glass transition point (Tg) of this toner was determined in the same manner as in Example 4-1.
69 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 15.42 ° C.

Further, the above-described blocking test of the toner was carried out in the same manner as in Example 4-1. As a result, the toner retained good fluidity and had good blocking resistance. Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1. Using this developer, an image for fixing property evaluation was prepared in the same manner as in Example 4-1. , Fixability was evaluated. As a result, the particle shape could not be confirmed, and the fixability was good (see Table 9).

Example 4-9 A toner was prepared in the same manner as in Example 4-1 except that the styrene monomer was changed to 120 parts by mass and butyl acrylate was changed to 30 parts by mass. Particles were created. The number average particle diameter of the obtained toner particles was measured in the same manner as in Example 4-1 and found to be 6.32 μm. The toner particles were coated with a sol-gel film in the same manner as in Example 4-1 to obtain a toner of this example. The number average particle diameter of the obtained toner was 6.44 μm.

When the particle surface of this toner was observed with a scanning microscope photograph, a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer formed by fixation of granular lumps containing at least a silicon compound on the surface of the particles of the toner was confirmed.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the proportion of silicon atoms is 4.
It was 80% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner obtained in the same manner was 100%, the content ratio of silicon atoms was 0.05% by mass. Therefore, the abundance of silicon atoms on the particle surface of the toner is 99.93 times the abundance of silicon atoms on the cross section of the toner particle, and the polycondensate of the silicon compound is mostly present on the particle surface of the toner. However, it was found that it hardly existed inside the toner particles.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surface of the toner was 3.61% by mass. Therefore, the reduction ratio of silica existing on the surface of the toner particles before and after the surfactant was washed was 24.78%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together.

The melting start temperature of the toner obtained as described above was measured using the same method as in Example 4-1 and found to be 104.40 ° C. The glass transition point (Tg) of this toner was found to be 64.18 ° C. by the same method as in Example 4-1. The difference between the melting start temperature and the glass transition point of this toner was 40.22 ° C. Was.

Further, the toner obtained above was subjected to a blocking test in the same manner as in Example 4-1. As a result, the fluidity of the toner was good, and the blocking resistance was good. Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1. Using this developer, an image for fixing property evaluation was prepared in the same manner as in Example 4-1. , Fixability was evaluated. As a result, an average of 6.7 particles were observed in one visual field, but there was no problem in fixability. This is because the amount of coating of the coating layer formed by the fixation of the granular lumps containing at least the silicon compound of the toner is excessive, so that a sufficient heat fixing property is obtained in the fixing property test performed in the present invention. Probably because there was no.

Example 4-10 <Preparation of Base Toner Particles> First, base toner particles were prepared by the following method. High-speed stirrer T
1000 parts by mass of ion-exchanged water and 45 parts by mass of polyvinyl alcohol are added to a four-necked flask equipped with a K-homomixer, the number of revolutions of the stirrer NO is adjusted to 3000 pm, and the mixture is heated to 55 ° C. to prepare a dispersion medium. did.

On the other hand, a monomer dispersion was prepared as follows. 3 parts by mass of styrene polymer 20 parts by mass of n-butyl acrylate monomer 5 parts by mass of carbon black 0.5 part by mass of metal salicylate compound 8 parts by mass of release agent (paraffin wax 155) 8 parts by mass After the mixture was dispersed for 3 hours, 1.4 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added, and this dispersion was charged into the above-described dispersion medium. Granulation was performed for 10 minutes while maintaining the rotation speed. Then, at 50 rpm, 55 ° C for 1 hour, 65
Polymerization was carried out at 4 ° C. for 4 hours and further at 80 ° C. for 5 hours.

After completion of the polymerization, the slurry was cooled, and the dispersant was removed by repeating washing with purified water. Further washing and drying were performed to obtain toner particles serving as a base. The number average particle diameter of the toner particles measured by the same method as in Example 4-1 was 5.02 μm. Further, when the glass transition point (Tg) of the toner particles was measured, it was 27.8.
6 ° C.

<Preparation of Coating Layer (Sol-Gel Film)> The procedure was carried out except that the amount of tetraethoxysilane used was changed from 2.5 parts by mass to 10 parts by mass using the toner particles serving as the base obtained above. In the same manner as in Example 4-1, a coating layer formed by fixing at least granular lumps containing a silicon compound to toner particles was coated. As a result, the number average particle diameter of the obtained toner of this example was measured by the same method as in Example 4-1 and found to be 6.32 μm.

When the particle surface of this toner was observed with a scanning microscope photograph, a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer was formed on the surface of the particles of the toner.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the content ratio of silicon atoms is 2%.
It was 0.49% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner similarly determined was 100%, the abundance ratio of silicon atoms was 1.70% by mass. This coating layer can be said to be a coating layer having a relatively large coating amount. From the above measurement values, the abundance of silicon atoms on the particle surface of the toner is 12.08 times the abundance of silicon atoms on the cross section of the toner particle, and the polycondensate of the silicon compound is present to some extent inside the toner particle. I knew I was doing it.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surface of the toner was 14.86% by mass.
Accordingly, the reduction ratio of silica present on the surface of the toner particles before and after the surfactant was washed was 27.48%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together.

The melting start temperature of the toner obtained as described above was measured using the same method as in Example 4-1 and found to be 142.40 ° C. The glass transition point (Tg) of this toner determined by the same method as in Example 4-1 was 34.55 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 107.9 ° C.

Further, the above toner blocking test was conducted in the same manner as in Example 4-1. As a result, the fluidity of the toner was good, and the blocking resistance was good. Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1. Using this developer, an image for fixing property evaluation was prepared in the same manner as in Example 4-1. , Fixability was evaluated. As a result, an average of 7.9 particles were observed in one visual field, but there was no problem in fixability. This is probably because the coating amount on the toner was relatively large, and a polycondensate of the silicon compound was also present inside the toner, so that a sufficient heat fixing property was not obtained in the fixing property test in the present invention. It seems to be.

[Example 4-11] In coating the sol-gel film in Example 4-1, after reacting at room temperature for 2 days, the particles were filtered without adding alcohol to the system, and then the toner was coated. After the particle surface was washed, it was heated in a dryer at 50 ° C. overnight to obtain a toner. The number average particle diameter of the obtained toner was measured by the same method as in Example 4-1.
6.25 μm.

When the particle surface of this toner was observed with a scanning microscope photograph, a coating layer having fine granular irregularities having a diameter of about 40 nm was observed on the particle surface of the toner. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that a coating layer formed by fixation of granular lumps containing at least a silicon compound on the surface of the particles of the toner was confirmed.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the proportion of silicon atoms is 6.
It was 05% by mass. Similarly, when the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner was determined to be 100%, the abundance ratio of silicon atoms was 5.32% by mass. Therefore, the amount of silicon atoms present on the particle surface of the toner is 1.14 times the amount of silicon atoms present on the cross section of the toner particles. It turned out that things existed.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surface of the toner was 4.55% by mass.
Accordingly, the reduction ratio of silica present on the toner particle surface before and after the surfactant was washed was 24.78%. Therefore, it was confirmed that this toner had a coating layer formed by fixing the granular lumps together.

The melting start temperature of the toner obtained as described above was measured using the same method as in Example 4-1 and found to be 99.57 ° C. The glass transition point (Tg) of the toner was determined by the same method as in Example 4-1 and found to be 35.83 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 63.74 ° C.

Further, when the above-described blocking test of the toner was performed in the same manner as in Example 4-1, the fluidity of the toner was good and the blocking resistance was good.
Using the toner, a two-component developer was prepared in the same manner as in Example 4-1. Using this developer, an image for fixing property evaluation was created in the same manner as in Example 4-1. The fixability was evaluated. As a result, an average of 8.5 particles were observed in one visual field, but there was no problem in fixability. This is probably due to the fact that the polycondensate of the silicon compound is present inside the toner, so that the fixability was slightly lowered (see Table 9).

[Comparative Example 4-1] The polymerized black toner particles used in Example 4-1 were coated with at least a coating layer formed by fixing at least granular particles containing a silicon compound. The toner of this comparative example was used. The glass transition point of the particles was 2 as described in Example 4-1.
7.86 ° C. The melting start temperature of this toner was measured using the same method as in Example 4-1.
89 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 5.03 ° C.

Further, when the above-described blocking test of the toner was performed in the same manner as in Example 4-1, the toner was completely melted and fixed to the bottom of the sample bottle in the form of a film. Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1. Using this developer, an image for fixing property evaluation was prepared in the same manner as in Example 4-1. However, toners fused together in the stirrer, making it impossible to form a sufficient image (see Table 9).

Comparative Example 4-2 A toner was prepared in the same manner as in Example 4-1 except that the amount of tetraethoxysilane was changed to 0.1 part by mass. The number average particle diameter of the obtained toner was measured in the same manner as in Example 4-1. As a result, it was 6.35 μm. When the particle surface of this toner was observed with a scanning microscope photograph, no irregularities due to the silica coating layer could be confirmed on the particle surface of the toner. Further, the transmission electron micrograph of the cross section of the particles of this toner was observed in the same manner, and a coating layer formed by fixing at least the granular lumps containing the silicon compound could not be confirmed.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the content ratio of silicon atoms is 0.1%.
It was 09% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner determined similarly was 100%, the abundance ratio of silicon atoms was 0.02% by mass.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 0.07% by mass. Therefore, the reduction ratio of silica present on the toner particle surface before and after the surfactant was washed was 30.15%. From the above results, although the existence of silica atoms was confirmed, this toner did not have a coating layer formed by fixing at least the granular lumps containing the silicon compound.

The melting start temperature of the toner obtained as described above was measured using the same method as in Example 4-1 and found to be 49.15 ° C. The glass transition point (Tg) of this toner was found to be 28.74 ° C. by the same method as in Example 4-1. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 20.41 ° C.

Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surface of the toner was 2.85% by mass.
Accordingly, the reduction ratio of silica present on the toner particle surface before and after the surfactant was washed was 22.14%. From the above results, although this toner has a coating layer containing a silicon compound, the surface of the coating layer is smooth and is clearly different from the coating layer formed by fixing the granular masses. I understood.

The melting start temperature of the toner obtained as described above was measured by the same method as in Example 4-1 and found to be 106.21 ° C. The glass transition point (Tg) of this toner determined by the same method as in Example 4-1 was 28.55 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 77.66 ° C.

Further, the above toner blocking test was conducted in the same manner as in Example 4-1. As a result, the fluidity of the toner was good, and the blocking resistance was good.
Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1.
An image for fixing property evaluation was prepared in the same manner as in the above, and the fixing property was evaluated. As a result, most of the particles were not fixed, and the particle shape was maintained. This is probably
Since the surface of the toner particles is smooth, heat conduction is poor, and it is considered that the fixing property test performed in the present invention did not show sufficient fixing property.

[Comparative Example 4-3] With respect to 100 parts by mass of the toner particles serving as the base used in Example 4-1, 0.50 part by mass of a room-temperature-curable silicone resin was added and charged into a sample bottle. And stir on a roll mill for 30 minutes.
By continuing stirring for 3 hours in an atmosphere of 0 ° C., a toner coated with a silicone resin was obtained. The number average particle size of the obtained toner was 6.63 μm.

When the surface of the toner particles was observed with a scanning microscope photograph, the surface of the toner particles was smooth.
No particulate irregularities were observed. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, it was confirmed that some coating layer was formed on the surface of the particles of the toner.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the abundance ratio of silicon atoms is 3.
It was 66% by mass. When the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross section of the toner similarly determined was 100%, the abundance ratio of silicon atoms was 0.07% by mass. Therefore, the amount of silicon atoms present on the particle surface of the toner is 54.65 times the amount of silicon atoms present on the particle cross section, and the polycondensate of the silicon compound mainly exists on the particle surface of the toner. Was hardly present inside the particles.

Further, after the toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 2.85% by mass.
Accordingly, the reduction ratio of silica present on the toner particle surface before and after the surfactant was washed was 22.14%. From the above results, although this toner has a coating layer containing a silicon compound, the surface of the coating layer is smooth and is clearly different from the coating layer formed by fixing the granular masses. I understood.

The melting start temperature of the toner obtained as described above was measured by the same method as in Example 4-1 and found to be 106.21 ° C. The glass transition point (Tg) of this toner determined by the same method as in Example 4-1 was 28.55 ° C. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 77.66 ° C.

Further, the above toner blocking test was conducted in the same manner as in Example 4-1. As a result, the fluidity of the toner was good and the blocking resistance was good.
Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1.
An image for fixing property evaluation was prepared in the same manner as in the above, and the fixing property was evaluated. As a result, most of the particles were not fixed, and the particle shape was maintained. This is probably
Since the surface of the toner particles is smooth, heat conduction is poor, and it is considered that the fixing property test performed in the present invention did not show sufficient fixing property.

[Comparative Example 4-4] The average particle diameter was 40 with respect to 100 parts by mass of the base toner particles used in Example 4-1.
5 parts by mass of hydrophobized silica particles having a thickness of 10 nm were mixed and mixed with a Henschel mixer to externally add silica fine particles to obtain a toner. The number average particle diameter of the obtained toner was measured by the same method as in Example 4-1.
m.

When the particle surface of this toner was observed with a scanning microscope photograph, particles were found on the surface of the toner particles, but there were many gaps between the particles, and no film was observed. Was. Further, from observation of a cross section of the particles of the toner with a transmission electron microscope photograph, silica particles were observed on the surface of the particles of the toner, and it was confirmed that the silica particles were present individually.

When the total amount of carbon atoms, oxygen atoms, and silicon atoms on the particle surface of the toner determined by EPMA is 100%, the content ratio of silicon atoms is 0.1%.
It was 55% by mass. In addition, when the total amount of carbon atoms, oxygen atoms, and silicon atoms in the particle cross-section of the toner similarly determined was 100%, the abundance ratio of silicon atoms was 0.01% by mass. Further, after this toner was washed with a 5% aqueous solution of dodecylbenzenesulfonic acid, the amount of silicon atoms present on the particle surfaces of the toner was 0.37% by mass. Therefore, the reduction rate of silica present on the surface of the toner particles before and after the surfactant cleaning is 33.48.
%Met.

The melting start temperature of the toner obtained as described above was measured using the same method as in Example 4-1 and found to be 43.33 ° C. The glass transition point (Tg) of this toner was found to be 29.75 ° C. by the same method as in Example 4-1. Therefore, the difference between the melting start temperature and the glass transition point of this toner was 13.58 ° C.

Further, the above-described blocking test of the toner was carried out in the same manner as in Example 4-1. As a result, the toner was completely melted and fixed to the bottom of the bottle in a film form. Using the toner described above, a two-component developer was prepared in the same manner as in Example 4-1. Using this developer, an image for fixing property evaluation was prepared in the same manner as in Example 4-1. , Fixability was evaluated. As a result, no particle shape was confirmed. Table 8 below
Shows the characteristics of the toner particles and the toner in Examples 4-1 to 4-11 and Comparative examples 4-1 to 4-4, and Table 9 shows the evaluation results.

[0458]

[Table 8]

[0459]

[Table 9]

The blocking resistance in Table 9 was evaluated by placing 30 g of the toner particles in a 30 ml sample bottle, leaving the toner particles to stand in a thermostat at 50 ° C. for 2 days, and visually observing the state of the toner. The following criteria were used. A: Particles flow when the bottle is tilted. B: The particles flow when the bottle bottom is tapped lightly. C: When the bottle is tilted, the particles flow as a lump. D: Part of the particles melted and adhered to the bottle. E: The particles are completely melted and adhere to the bottom of the bottle in a film form.

The fixing property in Table 9 was determined by developing and fixing a solid image on an OHP sheet, and then observing whether or not the toner particle shape remained at a magnification of 1000 using a scanning microscope.
The results are shown by the following criteria. A: No particle shape is observed. B: There are 6 or less portions maintaining the particle shape per visual field. C: There are 10 or less parts per field of view maintaining the particle shape. D: Most of the particles maintain the particle shape.

[0462]

As described above, according to the present invention,
By providing a coating layer formed by fixing at least particles containing silicon compounds on the surface of the toner particles serving as a base, it exhibits excellent fluidity without using a fluidizing agent and is stable in durability. A toner that can maintain a high charge amount and that can form a good image and that can achieve high transfer efficiency is provided. Further, according to the present invention, since no fluidizing agent is used, even when continuous development is performed, the liberation of the fluidizing agent,
The present invention provides a toner that does not cause the fluidizing agent to be embedded in the toner particles, stably retains excellent fluidity in durability, and has excellent durability. Further, according to the present invention, there is provided a toner production method capable of easily and stably obtaining an excellent toner having the above-mentioned properties.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03G 9/08 375 381 384 (31) Priority claim number Japanese Patent Application No. 11-188209 (32) Priority date July 1999 1st (July 7.1) (33) Priority Country Japan (JP) (72) Inventor Yoshinobu Baba 3-30-2 Shimomaruko, Ota-ku, Tokyo Within Canon Inc. (72) Inventor Tamotsu Ayaki 3-3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yuzo Tokunaga 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Takeshi Ikeda Ota, Tokyo 3-30-2 Kumoshita Maruko F-term in Canon Inc. (reference) 2H005 AA01 AA06 AA08 AB03 AB06 AB10 CA04 CA08 CA14 CA26 CB13 DA05 EA03 EA05 EA07

Claims (76)

[Claims] 1. A toner comprising toner particles having at least a binder resin and a coloring agent, wherein a coating layer formed by fixing at least particles containing a silicon compound to the surface of the toner particles. A toner comprising: 2. The toner according to claim 1, wherein the silicon atom is present in an amount of 0.1 to 20.0% by mass based on the total amount of carbon atoms, oxygen atoms and silicon atoms measured by an electron probe microanalysis on the particle surface of the toner. The toner according to claim 1, wherein 3. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by an electron probe microanalysis on the particle surface of the toner is 0.1 to 10.0% by mass. The toner according to claim 1, wherein 4. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe micropartial analysis on the particle surface of the toner is 0.1 to 4.0% by mass. The toner according to claim 1, wherein 5. The method according to claim 1, wherein the ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microscopic analysis on the particle cross section is 4.0 mass% or less. Item 7. The toner according to Item 1. 6. The toner according to claim 1, wherein the ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms measured by electron probe microanalysis on the particle cross section is 0.1% by mass or less. Item 7. The toner according to Item 1. 7. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe micropartial analysis on the particle surface of the toner is 0.1 to 20.0% by mass. And the content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by an electron probe microanalysis on a particle cross section of the toner is 4.0% by mass.
The toner according to claim 1, wherein: 8. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 10.0% by mass. And the content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms measured by the electron probe microscopic analysis in the particle cross section of the toner is 0.1% by mass.
The toner according to claim 1, wherein: 9. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 4.0% by mass. Wherein the proportion of silicon atoms, based on the total amount of carbon atoms, oxygen atoms and silicon atoms, measured by electron probe microanalysis on the particle cross section of the toner is 0.1% by mass or less. Item 7. The toner according to Item 1. 10. The toner according to claim 1, wherein the abundance ratio of silicon atoms on the surface of the particles of the toner provided with the coating layer is at least twice the abundance ratio of silicon atoms on the cross section of the particles of the toner. Item 2. The toner according to item 1. 11. The toner according to claim 1, wherein the coating layer is formed of a polycondensate of a silicon compound. 12. The toner according to claim 11, wherein the polycondensate of the silicon compound is formed by a sol-gel method. 13. The toner according to claim 11, wherein the coating layer is in a state in which granular lumps containing a polycondensate of a silicon compound are chemically bonded to each other. 14. The binder resin is a styrene resin, an acrylic resin, a methacrylic resin, a polyester resin,
The toner according to any one of claims 1 to 13, further comprising a resin selected from the group consisting of a mixture thereof. 15. The toner according to claim 1, wherein the surface of the coating layer is treated with a coupling agent. 16. The toner according to claim 15, wherein the coupling agent can react with a silanol group present on the surface of the coating layer. 17. The toner has a number average particle diameter of 0.1.
The toner according to any one of claims 1 to 16, wherein the toner has a variation coefficient of a number distribution of from 1 μm to 10.0 μm and 20.0% or less. 18. The toner has a number average particle size of 1.0.
The toner according to claim 17, wherein the particle size is from μm to 8.0 μm. 19. The toner has a number average particle size of 3.0.
The toner according to claim 17, wherein the particle size is from μm to 5.0 μm. 20. The toner according to claim 17, wherein the toner has a coefficient of variation having a number distribution of 15.0% or less. 21. The toner according to claim 17, wherein the toner has a coefficient of variation with a number distribution of 10.0% or less. 22. The toner has at least one glass transition point at a temperature of at least 60 ° C. and a melting start temperature of 100 ° C.
22. The method according to claim 1, wherein a difference between the glass transition point and the melting start temperature is 38 ° C. or less.
Item. 23. The toner according to claim 22, wherein the toner further contains a release agent component in a range of 80% by mass or less. 24. A method for producing a toner comprising toner particles having a coating layer on the surface, comprising: a toner particle preparing step of preparing toner particles having at least a binder resin and a colorant; A coating layer that forms a coating layer formed by adhering at least particulate agglomerates containing a silicon compound to the surface of toner particles by depositing a polycondensate of a silicon compound on the surface of the toner particles from the outside. Forming a toner. 25. The method according to claim 25, wherein the coating layer forming step includes at least a binder resin and a colorant in an aqueous solvent in which a silicon compound is dissolved or in a mixed solvent of the aqueous solvent and water. To prepare a toner dispersion; and adding the dispersion in an alkaline aqueous solvent or in a mixed solvent of the alkaline aqueous solvent and water, and hydrolyzing the silicon compound by a hydrolysis reaction. 25. The toner according to claim 24, comprising: condensing the polycondensate from the outside to deposit the polycondensate on the surface of the toner particles to form a coating layer in which at least the granular lumps containing the silicon compound are fixed. Manufacturing method. 26. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 20.0% by mass. The method for producing a toner according to claim 24 or 25, wherein 27. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 10.0% by mass. The method for producing a toner according to claim 24 or 25, wherein 28. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by an electron probe microanalysis on the particle surface of the toner is 0.1 to 4.0% by mass. The method for producing a toner according to claim 24 or 25, wherein 29. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle cross section of the toner is 4.0 mass% or less. Item 24 or 25
3. The method for producing a toner according to item 1. 30. The toner according to claim 30, wherein the proportion of silicon atoms, based on the total amount of carbon atoms, oxygen atoms, and silicon atoms, measured by electron probe microanalysis on the particle cross section is 0.1% by mass or less. Item 24 or 25
3. The method for producing a toner according to item 1. 31. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 20.0% by mass. And the ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle cross section of the toner is 4.0% by mass or less. Item 29. The method for producing a toner according to Item 24 or 25. 32. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe micropartial analysis on the particle surface of the toner is 0.1 to 10.0% by mass. Wherein the proportion of silicon atoms, based on the total amount of carbon atoms, oxygen atoms and silicon atoms, measured by electron probe microanalysis on the particle cross section of the toner is 0.1% by mass or less. Item 29. The method for producing a toner according to Item 24 or 25. 33. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 4.0% by mass. And the content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms measured by the electron probe microscopic analysis in the particle cross section of the toner is 0.1% by mass.
The method for producing a toner according to claim 24, wherein: 34. The toner according to claim 24, wherein the abundance ratio of silicon atoms on the particle surface of the toner provided with the coating layer is at least twice the abundance ratio of silicon atoms on the cross section of the toner particle. 2. The method for producing a toner according to item 1. 35. The method according to claim 24, wherein the coating layer is formed of a polycondensate of a silicon compound. 36. The method according to claim 35, wherein the polycondensate of the silicon compound is formed by a sol-gel method. 37. The method for producing a toner according to claim 35, wherein the coating layer is in a state in which granular lumps containing a polycondensate of a silicon compound are chemically bonded to each other. 38. The binder resin is a styrene resin, an acrylic resin, a methacrylic resin, a polyester resin,
The method for producing a toner according to any one of claims 24 to 37, further comprising a resin selected from the group consisting of a mixture thereof. 39. The method according to claim 24, wherein the surface of the coating layer is treated with a coupling agent. 40. The method according to claim 39, wherein the coupling agent is capable of reacting with a silanol group present on the surface of the coating layer. 41. The toner has a number average particle diameter of 0.1.
The method for producing a toner according to any one of claims 24 to 40, wherein the toner has a coefficient of variation having a number distribution of 1 μm to 10.0 μm and 20.0% or less. 42. The toner has a number average particle diameter of 1.0.
The method for producing a toner according to claim 41, wherein the particle diameter is from μm to 8.0 μm. 43. The toner has a number average particle size of 3.0.
The method for producing a toner according to claim 41, wherein the particle diameter is from μm to 5.0 μm. 44. The method according to claim 41, wherein the toner has a number distribution variation coefficient of 15.0% or less. 45. The method according to claim 41, wherein the toner has a coefficient of variation of a number distribution of 10.0% or less. 46. In the toner particle preparation step, at least the polymerizable monomer is dissolved in a solvent in which a polymerizable monomer for forming a binder resin is dissolved but the polymer is not dissolved. The method for producing a toner according to any one of claims 41 to 45, wherein toner particles having at least a binder resin and a colorant are prepared by polymerizing the polymerizable monomer therein. 47. A polymerizable monomer for synthesizing the binder resin is soluble, but the polymer is at least dissolved in a solvent in which the polymer cannot be dissolved. Producing a toner particle containing at least a binder resin and a colorant by polymerizing the polymerizable monomer, and preparing a toner dispersion in which the toner particle is dispersed; and Alternatively, the dispersion is added to a mixed solvent of the alkaline aqueous solvent and water, and the polycondensate is deposited on the surface of the toner particles by polycondensing the silicon compound by a hydrolysis reaction. The method for producing a toner according to any one of claims 41 to 45, further comprising: forming a coating layer in which granular lumps containing at least a silicon compound are fixed to each other. 48. A polymerizable monomer for synthesizing the binder resin can be dissolved, but the polymer is dissolved in a solvent in which the polymer cannot be dissolved. Producing a toner particle containing at least a binder resin and a colorant by polymerizing the polymerizable monomer, and preparing a toner dispersion in which the toner particle is dispersed; and After cooling to room temperature, at least a silicon compound and an alkali are added to the cooled toner dispersion, and the silicon compound is polycondensed by a hydrolysis reaction, whereby the polycondensate is externally deposited on the surface of the toner particles. The method for producing a toner according to any one of claims 41 to 45, further comprising: forming a coating layer in which granular lumps containing at least a silicon compound are fixed to each other. 49. The toner has at least one glass transition point at a temperature of at least 60 ° C. or lower and a melting start temperature of 100 ° C.
49. The method for producing a toner according to any one of claims 24 to 48, wherein the difference between the glass transition point and the melting start temperature is 38 ° C or less. 50. The method according to claim 49, wherein the toner further contains a release agent component in a range of 80% by mass or less. 51. A method for producing a toner composed of toner particles having a coating layer on the surface, comprising preparing at least toner particles containing at least a binder resin and a colorant and containing a silicon compound. A step of preparing toner particles; and subjecting the toner particles to a hydrolysis and polycondensation reaction of a silicon compound on the surface of the toner particles in a liquid selected from the group consisting of water and a mixed solvent of water and an aqueous solvent. A step of forming a coating layer in a state in which granular masses containing at least a silicon compound are fixed to the surface of the toner particles. 52. The toner particle preparation step, wherein at least a binder resin and a colorant are contained in a liquid selected from the group consisting of water and a mixed solvent of water and an aqueous solvent, and the silicon compound Preparing a toner particle dispersion by dispersing toner particles not containing
And dispersing at least a silicon compound in a liquid selected from the group consisting of a mixed solvent of water and an aqueous solvent to prepare a silicon compound dispersion; and adding the toner particle dispersion to the silicon compound dispersion 52. The method according to claim 51, further comprising the step of swelling the silicon compound in the toner particles and causing the silicon compound to be present in the toner particles. 53. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 20.0% by mass. The method for producing a toner according to claim 51 or 52, wherein 54. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 10.0% by mass. The method for producing a toner according to claim 51 or 52, wherein 55. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe micropartial analysis on the particle surface of the toner is 0.1 to 4.0% by mass. The method for producing a toner according to claim 51 or 52, wherein 56. The toner according to claim 56, wherein the proportion of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle cross section is 4.0% by mass or less. Item 51 or 52
3. The method for producing a toner according to item 1. 57. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by an electron probe microanalysis on the particle cross section of the toner, wherein the ratio of silicon atoms is 0.1% by mass or less. Item 51 or 52
3. The method for producing a toner according to item 1. 58. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe micropartial analysis on the particle surface of the toner is 0.1 to 20.0% by mass. And the ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle cross section of the toner is 4.0% by mass or less. Item 51. The method for producing a toner according to Item 51 or 52. 59. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 10.0% by mass. Wherein the proportion of silicon atoms, based on the total amount of carbon atoms, oxygen atoms and silicon atoms, measured by electron probe microanalysis on the cross section of the particles of the toner is 0.1% by mass or less. Item 51. The method for producing a toner according to Item 51 or 52. 60. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms measured by electron probe microanalysis on the particle surface of the toner is 0.1 to 4.0% by mass. And the content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms measured by the electron probe microscopic analysis in the particle cross section of the toner is 0.1% by mass.
The method for producing a toner according to claim 51 or 52, wherein: 61. The content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms and silicon atoms measured by electron probe micropartial analysis on the particle surface of the toner is 0.1 to 4.0% by mass. And the content ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms measured by the electron probe microscopic analysis in the particle cross section of the toner is 0.1% by mass.
The method for producing a toner according to claim 51 or 52, wherein: 62. The toner according to claim 51, wherein the abundance ratio of silicon atoms on the particle surface of the toner provided with the coating layer is at least twice the abundance ratio of silicon atoms on the cross section of the toner particle. 2. The method for producing a toner according to item 1. 63. The method according to claim 51, wherein the coating layer is formed by a polycondensate of a silicon compound. 64. The method according to claim 63, wherein the polycondensate of the silicon compound is formed by a sol-gel method. 65. The method for producing a toner according to claim 63, wherein the coating layer is in a state in which granular lumps containing a polycondensate of a silicon compound are chemically bonded to each other. 66. The binder resin, wherein the binder resin is a styrene resin, an acrylic resin, a methacrylic resin, a polyester resin,
The method for producing a toner according to any one of claims 51 to 65, further comprising a resin selected from the group consisting of a mixture thereof. 67. The method according to claim 51, wherein the surface of the coating layer is treated with a coupling agent. 68. The method according to claim 67, wherein the coupling agent is capable of reacting with a silanol group present on the surface of the coating layer. 69. The toner has a number average particle diameter of 0.1.
69. The method for producing a toner according to any one of claims 51 to 68, wherein the toner has a coefficient of variation of 20.0% or less and a particle size of 1 μm to 10.0 μm. 70. The toner has a number average particle diameter of 1.0.
The method for producing a toner according to claim 69, wherein the particle diameter is from μm to 8.0 μm. 71. The toner has a number average particle size of 3.0.
The method for producing a toner according to claim 69, wherein the particle diameter is from μm to 5.0 μm. 72. The method according to claim 69, wherein the toner has a number distribution variation coefficient of 15.0% or less. 73. The method according to claim 69, wherein the toner has a coefficient of variation of a number distribution of 10.0% or less. 74. In the toner particle preparation step, at least the polymerizable monomer is dissolved in a solution in which a polymerizable monomer for forming a binder resin is dissolved but the polymer is not dissolved. 74. The method for producing a toner according to any one of claims 69 to 73, wherein toner particles having at least a binder resin and a colorant are prepared by polymerizing the polymerizable monomer in a solvent. 75. The toner has at least one glass transition point at a temperature of 60 ° C. or less and a melting start temperature of 100 ° C.
75. The method for producing a toner according to any one of claims 51 to 74, wherein the difference between the glass transition point and the melting start temperature is 38 ° C or less. 76. The method according to claim 75, wherein the toner further contains a release agent component in a range of 80% by mass or less.