JP2002365854A - Toner, method for forming image and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner with high transfer efficiency and little production of waste toner. SOLUTION: The toner containing at least a binder resin and a coloring agent is characterized in that it contains a sulfur-containing compound selected from a group composed of sulfur containing polymers and sulfur containing copolymers. The weight average particle size of the toner ranges from 5 to 12 μm and the circularity of the particles having >=3 μm particle size in the toner is specified.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or a toner jet recording method, an image forming method using the toner, and Regarding process cartridge.

[0002]

2. Description of the Related Art As an electrophotographic method, US Pat.
A number of methods are known as described in Japanese Patent No. 7691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electrostatic latent image on the photoconductor by various means.
Then, the latent image is developed with toner, and the toner image is transferred to a transfer material such as paper, if necessary, and then fixed by heating, pressure, heating pressure, solvent vapor or the like to obtain a toner image.

In recent years, with the multi-functionalization of copying machines and printers, the higher image quality of copied images, and higher speeds, the performance required for toner has become more severe, and the toner has a finer particle size. As for particle size distribution,
A sharp product that does not contain coarse particles and has a small amount of ultrafine powder is required.

Although the resolution and sharpness of the image can be increased by making the toner finer, various problems arise.

First, by reducing the toner particle size, the specific surface area of the toner is increased, so that the width of the charge amount distribution is increased, and fogging of the toner on the non-image area is likely to occur. Further, the charging characteristics of the toner are more likely to be affected by the environment. To reduce the fog, it has been attempted to sharpen the toner particle size distribution,
This causes a cost increase due to a decrease in yield in toner production.

Further, due to the finer toner particles, the dispersibility of the binder resin and other internal additives is likely to affect the toner performance.

In order to solve such problems, a charge control agent is added to the toner in order to impart a desired triboelectric charge to the toner.

As charge control agents known in the art today, as negative triboelectric charge control agents, metal complex salts of monoazo dyes, metal complex salts of hydroxycarboxylic acids, dicarboxylic acids, aromatic diols, acids, etc. Resins containing components are known. As a positive triboelectric charge control agent, nigrosine dyes, azine dyes, triphenylmethane dyes and pigments, polymers having a quaternary ammonium salt and a quaternary ammonium salt in their side chains are known.

However, most of these charge control agents are colored and many cannot be used for color toners.

Further, some charge control agents have the following drawbacks. It is difficult to balance image density and fog. It is difficult to obtain sufficient image density in a high humidity environment. Poor dispersibility in resin. Storage stability, fixability and offset resistance are adversely affected.

In recent years, charge control agent resins have been studied from the viewpoints of triboelectric charge control and safety. JP-A-6
In 3-184762, a styrene-based monomer and 2-
A method of using a polymer of acrylamido-2-methylsulfonic acid is disclosed. Japanese Unexamined Patent Publication (Kokai) No. 3-161761 discloses a method in which a polymer of a styrene monomer and 2-acrylamido-2-methylsulfonic acid is used as a charge control agent for a polyester resin. Japanese Patent Laid-Open No. 2000-56518 discloses a toner containing a sulfonic acid group-containing (meth)acrylamide copolymer having a specific glass transition temperature as a charge control agent. Although these methods have excellent triboelectrification properties,
It cannot be said that it is sufficient in terms of handling environmental changes, aging, and usage conditions associated with finer toner particles, particularly improving image quality, and improving transfer efficiency in consideration of environmental problems described later.

When the toner image is transferred from the photosensitive member to the transfer material during the above steps, the transfer residual toner remains on the photosensitive member.

In order to quickly perform continuous copying, it is necessary to clean the residual toner on the photosensitive member. Further, the residual toner recovered is put into a container or a recovery box installed in the main body and then discarded, or is recycled through a circulation process.

In order to tackle environmental problems, it is necessary to design a recycling system inside the main body as a waste tonerless system.

However, in order to achieve multi-functionality of the copying machine and printer, high image quality of the copied image, and further speeding up, a considerably large-scale recycling system is required in the main body, and the copying machine and printer itself become large. Therefore, it cannot be miniaturized from the viewpoint of space saving.
The same applies to a system in which the waste toner is stored in a container or a collection box installed in the main body, or a system in which the photoconductor and the above-mentioned part for collecting the waste toner are integrated.

In order to meet these requirements, it is necessary to improve the transfer rate when the toner image is transferred onto the transfer material from the photosensitive member.

In JP-A-9-26672, a transfer efficiency improver having an average particle diameter of 0.1 to 3 μm and a hydrophobic silica fine powder having a BET specific surface area of 50 to 300 m ² /g are contained to obtain a toner volume. A method of reducing the resistance and improving the transfer efficiency by forming a thin film layer of the transfer efficiency improving agent on the photoconductor is disclosed. However, since the toner produced by the pulverization method has a particle size distribution, it is difficult to exert an effect uniformly on all particles, and further improvement is required.

As a method for improving the transfer efficiency, a toner obtained by a manufacturing method such as a spray granulation method, a solution dissolution method, and a polymerization method, which makes the shape of the toner closer to a spherical shape, is disclosed in JP-A-3-84558 and JP-A-3-84558. No. 229268, JP-A No. 4-1766, and JP-A No. 4-102862. However, not only large-scale equipment is required for manufacturing these toners, but also problems relating to cleaning are likely to occur because the toner approaches a true sphere.

Generally, as a method for producing a toner, a binder resin for fixing it on a transfer material, various colorants for giving a tint as a toner, and a charge control agent for imparting an electric charge to particles are used as raw materials. Alternatively, in the one-component developing method disclosed in JP-A-54-42141 and JP-A-55-18656, in addition to these, various magnetic materials for imparting transportability to the toner itself are used. .. Further, if necessary, other additives such as a release agent and a fluidity-imparting agent are added and dry-mixed, followed by melt-kneading with a general-purpose kneading device such as a roll mill and an extruder, and after cooling and solidifying, The kneaded product is atomized by various pulverizers such as a jet stream type pulverizer and mechanical collision type pulverizer, and the obtained coarse pulverized product is introduced into various wind classifiers to perform classification, thereby obtaining a particle size required as a toner. The toner particles are prepared, and if necessary, a fluidizing agent and a lubricant are externally added and dry mixed to obtain a toner. In the case of a two-component developer, various magnetic carriers and the above toner are mixed and used.

As described above, in order to obtain fine toner particles, conventionally, the method shown in the flow chart of FIG. 10 is generally adopted.

The crushed toner particles are continuously or sequentially supplied to the first classifying means, and the classified coarse particles containing a coarse particle group having a prescribed particle size or more as a main component are sent to the crushing means and crushed,
It is recycled to the first classifying means again.

The finely pulverized toner particles having other particles within the specified particle size range and particles having the specified particle size or less as the main components are sent to the second classifying means and mainly contain the particles having the specified particle size. The powder is classified into a powder and a fine powder whose main component is a particle group having a specified particle size or less. However, since the toner is made into fine particles, electrostatic agglomeration between the particles is increased, and the toner originally sent to the second classifying means is circulated again to the first classifying means, resulting in over-pulverized fine powder and ultrafine particles. Fine powder is easily generated.

Various crushing devices may be used as the crushing means. To crush the coarsely crushed toner mainly composed of the binder resin,
A jet stream type pulverizer using a jet stream as shown in FIG. 13, particularly a collision type air stream pulverizer is used.

A collision type air flow crusher using a high pressure gas such as a jet air stream conveys the powder raw material by a jet air stream and jets the powder raw material from the outlet of the accelerating pipe to face the opening surface of the outlet of the accelerating pipe. Then, the powder raw material is crushed by the collision force of the collision member thus provided and the impact force.

In the collision type air flow crusher shown in FIG. 13, the outlet 1 of the acceleration pipe 162 to which the high pressure gas supply nozzle 161 is connected.
A collision member 164 is provided so as to face 63, and the high-pressure gas supplied to the acceleration pipe 162 sucks the powder raw material into the acceleration pipe 162 from the powder raw material supply port 165 that is in communication with the middle of the acceleration pipe 162. The body material is ejected together with the high-pressure gas to collide with the collision surface 166 of the collision member 164 and is crushed by the impact, and the pulverized material is discharged from the pulverization chamber 168 into the pulverized material discharge port
It is discharged from 67.

However, since the above-mentioned collision type air flow pulverizer is constructed such that the powder raw material is ejected together with the high pressure gas to collide with the collision surface of the collision member and is pulverized by the impact, the pulverized toner particles are The shape is irregular and square.

In Japanese Patent Application Laid-Open No. 2-87157, a toner produced by a pulverization method is mechanically impacted (hybridizer).
Discloses a method of improving transfer efficiency by modifying the shape and surface property of particles. However, this method is not a preferable method because it requires a further processing step after pulverization, so that the toner surface approaches a state where there is no unevenness due to toner productivity and processing, and improvement on the developing surface is required.

As the classifying means, various airflow classifiers and methods have been proposed. Among them, there are classifiers that use rotary blades and classifiers that have no moving parts. Among these, there are a fixed wall centrifugal classifier and an inertial force classifier as classifiers having no moving parts. A classifier utilizing such inertial force is disclosed in Japanese Examined Patent Publication No. 54-24745 and Japanese Examined Patent Publication No. 55-64.
No. 33, and Japanese Patent Laid-Open No. 63-101858.

As shown in FIG. 8, these air flow type classifiers eject powder into the classifying area together with the air flow at a high speed from a supply nozzle having an opening in the classifying section of the classifying machine chamber, and a Coanda in the classifying chamber. The coarse powder, the medium powder, and the fine powder are separated by the centrifugal force of the curved airflow flowing along the block 145, and the coarse powder, the medium powder, and the fine powder are classified by the edges 146 and 147 with the thin tips. ing.

In the conventional classifying device 57, the finely pulverized raw material is introduced from the raw material supply nozzle, and the granular material flowing inside the pyramidal cylinders 148 and 149 tends to flow straight in parallel with the tube wall with a propulsive force. However, when the raw material is introduced from above in the raw material supply nozzle, it is roughly divided into an upper flow and a lower flow, and the upper flow contains a large amount of light fine powder and the lower flow contains a large amount of heavy coarse powder. Since each particle flows independently, different trajectories are drawn depending on the site of introduction into the classifier, and coarse powder disturbs the trajectory of fine powder, which limits the improvement of classification accuracy. Moreover, the accuracy tends to decrease in the classification of powder having a large number of coarse particles of 20 μm or more.

In general, toners are required to have many different properties, and in order to obtain such required properties, it is often determined by the manufacturing method as well as the raw materials used. In the toner classification step, classified particles are required to have a sharp particle size distribution. Further, it is desired to produce a high-quality toner efficiently and stably at low cost.

Further, in order to improve the image quality in a copying machine or a printer, the toner has a finer particle size,
The particle size distribution is required to be sharp without containing coarse particles and containing few ultrafine particles. Generally, as the substance becomes finer, the action of the interparticle force increases, but the same applies to the resin and the toner, and when it becomes a fine powder size, the cohesiveness of the particles increases.

Particularly when an attempt is made to obtain a toner having a sharp particle size distribution with a weight average diameter of 10 μm or less, the conventional apparatus and method cause a reduction in classification yield. Furthermore, when it is desired to obtain a toner having a sharp particle size distribution with a weight average diameter of 8 μm or less, not only the conventional apparatus and method cause a decrease in classification yield, but also a large amount of ultrafine powder is contained. There is a tendency to fall.

Further, in the finely divided toner, the compatibility of the individual materials contained in the toner becomes relatively important,
The developability will also be severer than before.

That is, for the purpose of reducing the transfer residual toner on the photoconductor, which is waste toner including the productivity of the toner itself, there is a demand for a highly developable toner with improved transfer efficiency.

[0036]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner having a high transfer efficiency with less generation of waste toner.

An object of the present invention is to provide a toner capable of maintaining good developability even when made into fine particles.

An object of the present invention is to provide a toner which is not affected by the image forming environment and which can maintain good developability even under high temperature and high humidity and room temperature and low humidity.

An object of the present invention is to provide a highly productive toner which can be easily manufactured by a pulverization method.

An object of the present invention is to provide an image forming method using the above toner.

An object of the present invention is to provide a process cartridge having the above toner.

[0042]

[In the formula, L ₀ represents the perimeter of a circle having the same projected area as the particle image, and L represents the perimeter of the particle image. ]

In addition, a) the relationship between the cut rate Z and the toner weight average diameter X satisfies the following expression (2), and the cut rate Z≦5.3×X (2) [where the cut rate Z is a flow manufactured by Toa Medical Electronics Co., Ltd. When the particle concentration A (number/μl) of all the measured particles measured by the formula particle image analyzer FPIA-1000 and the measured particle concentration B (number/μl) of the circle-equivalent diameter of 3 μm or more are expressed by the following formula (3): Shown. Z=(1−B/A)×100 (3)], and in particles of 3 μm or more of the toner, the circularity (a) of 0.950 or more in the number-based circularity distribution of the circularity (a). The relationship between the number-based cumulative value Y of the particles having the average particle size X and the toner weight average diameter X satisfies the following formula (4): The number-based cumulative value Y of the particles having a circularity of 0.950 or more Y≧exp5.51×X ^−0.645 ( 4) [However, the weight average particle diameter X of the toner is X: 5.0 to 12.0.
μm] or b) The relationship between the cut rate Z and the toner weight average diameter X satisfies the following formula (5), and the cut rate Z>5.3×X (5) and the toner particles having a diameter of 3 μm or more are circular. In the number-based circularity distribution of the degree (a), the relationship between the number-based cumulative value Y of the particles having the circularity (a) of 0.950 or more and the toner weight average diameter X satisfies the following expression (6). Relates to a toner. Number-based cumulative value of particles having a circularity of 0.950 or more Y≧exp 5.37×X ^−0.545 (6) [However, weight average particle diameter X of toner: 5.0 to 12.0]
μm]

Further, in the present invention, an electrostatic charge image is formed on the electrostatic charge image carrier, the electrostatic charge image is developed with the toner held in the developing means to form a toner image, and the formed toner image is formed. An image forming method in which a toner image on a transfer material is transferred to the transfer material via an intermediate transfer material or not, and the toner image on the transfer material is fixed to the transfer material by a heating and pressure fixing means. A toner having at least a colorant, the toner containing a sulfur-containing compound selected from the group consisting of a sulfur-containing polymer and a sulfur-containing copolymer, and the toner has a weight average particle diameter of 5 to 12 μm. In the particles of 3 μm or more of the toner, particles having a circularity a calculated by the following formula (1) of 0.900 or more have a number-based cumulative value of 90% by number or more, and the circularity a=L ₀ /L (1) [In the formula, L ₀ represents the perimeter of a circle having the same projected area as the particle image, and L represents the perimeter of the particle image. And a) the relationship between the cut ratio Z and the toner weight average diameter X satisfies the following formula (2), and the cut ratio Z≦5.3×X (2) [where the cut ratio Z is manufactured by Toa Medical Electronics Co., Ltd. When the particle concentration A (number/μl) of all the measured particles measured by the flow type particle image analyzer FPIA-1000 and the measured particle concentration B (number/μl) with an equivalent circle diameter of 3 μm or more are given by the following formula (3): Indicated by. Z=(1−B/A)×100 (3)], and in particles of 3 μm or more of the toner, the circularity (a) of 0.950 or more in the number-based circularity distribution of the circularity (a). The relationship between the number-based cumulative value Y of the particles having the average particle size X and the toner weight average diameter X satisfies the following formula (4): The number-based cumulative value Y of the particles having a circularity of 0.950 or more Y≧exp5.51×X ^−0.645 ( 4) [However, the weight average particle diameter X of the toner is X: 5.0 to 12.0.
μm] or b) The relationship between the cut rate Z and the toner weight average diameter X satisfies the following formula (5), and the cut rate Z>5.3×X (5) and the toner particles having a diameter of 3 μm or more are circular. In the number-based circularity distribution of the degree (a), the relationship between the number-based cumulative value Y of the particles having the circularity (a) of 0.950 or more and the toner weight average diameter X satisfies the following expression (6). The present invention relates to an image forming method. Number-based cumulative value of particles having a circularity of 0.950 or more Y≧exp 5.37×X ^−0.545 (6) [However, weight average particle diameter X of toner: 5.0 to 12.0]
μm]

Further, the present invention comprises an electrostatic charge image carrier, a developing means for developing the electrostatic charge image formed on the electrostatic charge image carrier with toner, and a container for holding dry toner. A process cartridge having at least the electrostatic charge image carrier, the developing means and the container, the process cartridge being detachably mountable to the main body of the image forming apparatus, and the toner being , Binder resin,
A toner having at least a colorant, wherein the toner is
Containing a sulfur-containing compound selected from the group consisting of a sulfur-containing polymer and a sulfur-containing copolymer, wherein the toner has a weight average particle diameter of 5 to 12 μm,
Among particles of m or more, particles having a circularity a calculated by the following formula (1) of 0.900 or more are 9 in terms of number-based cumulative value.
0 number% or more, circularity a=L ₀ /L (1) [wherein, L ₀ represents the perimeter of a circle having the same projected area as the particle image, and L represents the perimeter of the particle image. And a) the relationship between the cut ratio Z and the toner weight average diameter X satisfies the following formula (2), and the cut ratio Z≦5.3×X (2) [where the cut ratio Z is manufactured by Toa Medical Electronics Co., Ltd. When the particle concentration A (number/μl) of all the measured particles measured by the flow type particle image analyzer FPIA-1000 and the measured particle concentration B (number/μl) with an equivalent circle diameter of 3 μm or more are given by the following formula (3): Indicated by. Z=(1−B/A)×100 (3)], and in particles of 3 μm or more of the toner, the circularity (a) of 0.950 or more in the number-based circularity distribution of the circularity (a). The relationship between the number-based cumulative value Y of the particles having the average particle size X and the toner weight average diameter X satisfies the following formula (4): The number-based cumulative value Y of the particles having a circularity of 0.950 or more Y≧exp5.51×X ^−0.645 ( 4) [However, the weight average particle diameter X of the toner is X: 5.0 to 12.0.
μm] or b) The relationship between the cut rate Z and the toner weight average diameter X satisfies the following formula (5), and the cut rate Z>5.3×X (5) and the toner particles having a diameter of 3 μm or more are circular. In the number-based circularity distribution of the degree (a), the relationship between the number-based cumulative value Y of the particles having the circularity (a) of 0.950 or more and the toner weight average diameter X satisfies the following expression (6). Relates to a process cartridge. Number-based cumulative value of particles having a circularity of 0.950 or more Y≧exp 5.37×X ^−0.545 (6) [However, weight average particle diameter X of toner: 5.0 to 12.0]
μm]

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION The inventors of the present invention have studied the particle size and shape of toner and toner particles produced by a pulverization method, and have a circularity of 3 μm or more particles and transferability and developability (image quality). , And found that there is a close relationship with fixability.

Further, in order to exert the same effect on toners having different particle diameters, the toner weight average diameter and 3 μm are required.
It is necessary to control the circularity of particles of 3 μm or more by the following fine powder content.

By defining the circularity of the particles of 3 μm or more by the weight average diameter of the toner and the content of fine powder of 3 μm or less, it is possible to obtain a toner having excellent transferability, developability (image quality) and fixability.

Further, the toner of the present invention can be manufactured by a simple method which has never been used by using a specific crushing/classifying system.

Here, the pulverization/classification system capable of optimally producing the toner of the present invention is such that a mixture containing at least a binder resin, a colorant and a sulfur-containing compound is melt-kneaded, and the obtained kneaded product is cooled. The cooled raw material is roughly pulverized by a pulverizing means, and the powder raw material composed of the obtained coarse pulverized material is
Introduced into the constant quantity feeder, comprising at least a rotor consisting of a rotating body attached to the central rotation shaft, and a stator arranged around the rotor with a constant distance from the rotor surface, In addition, a predetermined amount of the powder raw material is fed from the first fixed amount feeder into the mechanical crusher configured so that the annular space formed by maintaining the space is airtight. The powder raw material is introduced through a body introduction port, and the rotor of the mechanical pulverizer is rotated at high speed to finely pulverize the powder raw material to have a weight average diameter of 5 to 12 μm and a particle diameter of 4.0 μm or less. A finely pulverized product having 70% by number or less of particles and 25% by volume or less of particles having a particle size of 10.1 μm or more is produced, and the pulverized pulverized product is discharged from a powder discharge port of a mechanical pulverizer. It is discharged and introduced into the second fixed quantity feeder, and a predetermined amount of finely pulverized material is introduced from the second fixed quantity feeder into the multi-divided airflow classifier that classifies the powder by the cross flow and Coanda effect. , Classifying the finely pulverized product into at least fine powder, medium powder and coarse powder in the multi-divided airflow classifier, mixing the classified coarse powder with the powder raw material, and introducing it into the mechanical pulverizer. It is a system that produces toner particles from the pulverized and classified medium powder. Details will be described later.

By reducing the toner particle size, the specific surface area of the toner particles increases. This increases the cohesiveness and adhesiveness of the toner. For this reason, when the toner image is transferred onto the transfer material from the photosensitive member via the intermediate transfer member or not, the adhesive force acting between the photosensitive member and the toner becomes strong, and the transfer efficiency is lowered. In particular, the toner produced by the conventional pulverization method becomes irregular and angular, and this tendency becomes more remarkable.

Even if the toner has a small particle diameter, it is possible to improve the transfer efficiency by providing the toner with the same low adhesion as the toner having the normal particle diameter or higher.

By making the toner spherical, it is possible to reduce the contact area between the toner and the photosensitive member and improve the transfer efficiency. However, it is very difficult to manufacture a true sphere toner with a pulverized toner. Therefore, a method has been considered in which the corners of the pulverized toner are removed and the surface is made smooth to bring it closer to this. This makes it possible to improve the transfer efficiency of the toner, but there are various problems due to the pulverization method, and it was necessary to further study.

When a toner having a small particle size is used, dot reproducibility is improved, but fog tends to occur, and scattering tends to occur. It is considered that this is because a large amount of fine powder and ultrafine powder are mixed in order to produce fine toner particles from coarsely crushed coarse particles. Toner particles with different particle diameters have different charging characteristics and different adhesion. Therefore, by reducing the particle size of the toner, the charge amount distribution of the toner becomes wider. Further, when the charge control agent added for the purpose of imparting charge to the toner is non-uniformly dispersed, this tendency becomes more remarkable.

By repeating classification of the toner particles produced by the pulverization method, a sharp particle size distribution can be obtained, but the productivity of the toner is lowered.

According to the study by the present inventor, in the toner particles produced by the pulverization method, the generation of waste toner is suppressed by improving the transfer rate when the toner image is transferred onto the transfer material from the photoconductor. In addition, in order to achieve good developability even under high temperature and high humidity and low humidity, in the toner particles having (1) a binder resin and a colorant, the toner particles are
By containing a sulfur-containing compound, the dispersibility with other materials can be improved to obtain a toner having a stable charge amount, and (2) the production in which a specific pulverizer and a specific classifier are combined. It is important that the toner having the toner particles produced by being pulverized and classified by an apparatus has a specific particle size distribution and circularity.

When the sulfur-containing compound is used, there is no problem if it is used as it is, but from the viewpoint of improving the compatibility when melt-kneading with other materials or improving the dispersibility when the toner particles are made into fine particles, It is preferable that the particles are crushed by a known crushing means to make the particle diameters uniform. The average particle size of the sulfur-containing compound is preferably 300 μm or less, more preferably 1
When the thickness is 50 μm or less, compatibility with other materials and dispersibility are further improved, and it is particularly effective in suppressing fog under low humidity.

In the case of producing a toner having a specific circularity, the weight average diameter is 5.0 to 12.0 μm, more preferably 40% by number or less of particles having a particle diameter of 4.0 μm or less. A toner having 25% by volume or less of particles of 10.1 μm or more is preferable.

To obtain a toner having a weight average diameter of more than 12.0 μm, the particle size can be dealt with by reducing the load in the crusher as much as possible or increasing the processing amount, but the shape is angular. It becomes difficult to obtain a desired circularity, and further it is difficult to obtain a desired circularity distribution.

To obtain a toner having a weight average particle diameter of less than 5.0 μm, the load in the crusher may be increased or the processing amount may be extremely reduced, but the shape is approximate to a sphere. However, it is difficult to obtain the desired circularity, and it is difficult to obtain the desired circularity distribution, and it becomes impossible to suppress the generation of fine powder/ultrafine powder. 4.0
The same applies to μm or less and 10.1 μm or more.

The toner is particles of 3 μm or more of the toner.
Where the circularity a calculated from the following equation (1) is 0.9
The number of particles of 00 or more is 90% or more in the cumulative value on the number basis, and the circularity a=L₀/L (1) [wherein L₀Is the perimeter of a circle with the same projected area as the particle image
And L represents the perimeter of the particle image. And a) the relationship between the cut rate Z and the toner weight average diameter X is
Satisfying (2), cut rate Z≦5.3×X (2) [where cut rate Z is a flow type particle image manufactured by Toa Medical Electronics Co., Ltd.
Of all measured particles measured by the analyzer FPIA-1000
Measurement of particle concentration A (number/μl), equivalent circle diameter of 3 μm or more
When the particle concentration is B (number/μl), the following formula (3) is used.
Shown. Z=(1−B/A)×100 (3)] and, in particles of 3 μm or more of the toner, circularity
In the number-based circularity distribution of (a), 0.950 or more
The number-based cumulative value Y of particles having the above circularity (a) and
The relationship of the weight average diameter X satisfies the following formula (4): Number-based cumulative value Y≧exp 5.51×X of particles having a circularity of 0.950 or more.^-0.645 (4) [However, toner weight average particle diameter X: 5.0 to 12.
0 μm] or b) The relationship between the cut rate Z and the toner weight average diameter X is expressed by the following formula.
Satisfaction (5), cut rate Z>5.3×X (5), and circularity in particles of 3 μm or more of the toner
In the number-based circularity distribution of (a), 0.950 or more
The number-based cumulative value Y of particles having the above circularity (a) and
The relationship of the weight average diameter X is the following formula (6): number-based cumulative value Y≧exp 5.37×X of particles having circularity of 0.950 or more^-0.545 (6) [However, toner weight average particle diameter X: 5.0 to 12.0
[μm] is preferable. The above exp5.
51 x X^-0.645Is e^5.51×X ^-0.645Is shown.

When the toner has such a circularity,
It is easy to control the charging of the toner, and it is possible to obtain uniform charging and durability stability. Further, it has been found that the transfer efficiency is increased when the circularity is as described above.
This is for toners with circularity as described above,
By reducing the contact area between the toner particles and the photoconductor,
This is because the adhesive force acting between the toner and the photoconductor is reduced.
Further, compared with the toner produced by the conventional collision type air flow pulverizer, the specific surface area of the toner particles is reduced, so that the contact area between the toner particles is reduced and the bulk density of the toner powder becomes dense. By improving the heat conduction during fixing,
The effect of improving fixability can also be obtained.

Further, when the presence of particles having a circularity a of 0.900 or more in particles of 3 μm or more of the toner is less than 90% in terms of the cumulative value on the number basis, the contact area between the toner particles and the photoconductor is Is increased, and the adhesion of the toner particles to the photoconductor is increased, which is not preferable because sufficient transfer efficiency cannot be obtained.

Particles having a circularity a of 0.950 or more among particles of 3 μm or more of the toner are cumulative values on a number basis, and the relationship between the cut rate Z and the toner weight average diameter X is cut rate Z≦5.3. ×X, preferably 0<cut rate Z
The number-based cumulative value Y≧exp5.51×X is satisfied, which satisfies the expression ≦5.3×X.
^-0.645 is not satisfied, that is, the number-based cumulative value Y<e
xp5.51×X ^−0.645 , or if the cut ratio Z>5.3×X is satisfied and the number-based cumulative value Y≧exp5.37×X
^-0.545 is not satisfied, that is, the number-based cumulative value Y<e
When xp 5.37×X ^−0.545 is satisfied, adhesion to a fixing member or the like is easily promoted, sufficient transfer efficiency may not be obtained, and toner fluidity may be deteriorated. Not preferable.

The standard deviation SD can also be used as one measure of the variation of particles having such circularity. In the present invention, the standard deviation SD of circularity is preferably 0.030 to 0.050, more preferably 0.0.
It is preferably 30 to 0.045.

The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles, and in the present invention, it is measured using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics. The circularity of the measured particles is determined by the following formula (1), and the sum of the circularity of all the particles measured by the following formula (5) is divided by the total number of particles to obtain the average circularity. Defined as degrees. Circularity a=L ₀ /L (1) [In the formula, L ₀ represents the perimeter of a circle having the same projected area as the particle image, and L represents the perimeter of the particle image. ]

[0066]

[Equation 1]

[0067]

[0068]

[Equation 2]

The circularity in the present invention is an index of the degree of unevenness of the toner and toner particles, and shows 1.00 when the toner is a perfect spherical shape, and the circularity becomes smaller as the surface shape becomes more complicated. Further, the SD of the circularity distribution in the present invention is an index of variation, and the smaller the numerical value, the sharper the distribution.

The measuring device "FP" used in the present invention
IA-1000" is a class obtained by calculating the circularity of each particle, and then calculating the average circularity and the standard deviation of circularity by dividing the circularity of 0.4 to 1.0 into 61 according to the obtained circularity. The calculation method of calculating the average circularity and the circularity standard deviation using the center value and frequency of the division points is used. However, each value of the average circularity and circularity standard deviation calculated by this calculation method, and each value of the average circularity and circularity standard deviation calculated by the calculation formula that directly uses the circularity of each particle described above. The error of is very small and can be substantially ignored. In the present invention, for the reason of handling data such as shortening of calculation time and simplification of calculation calculation formula, It is also possible to use the concept of the calculation formula that directly uses the circularity, and use such a partially modified calculation method.

As a concrete measuring method, 0.1 to 0.5 ml of a surfactant (preferably alkylbenzene sulfonate) as a dispersant is added to 100 to 150 ml of water in which impurities are removed in advance in a container, and further, Set the measurement sample to 0.
Add 1-0.5g. The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the dispersion liquid concentration is 1.
The circularity distribution of particles having a circle equivalent diameter of 0.60 μm or more and less than 159.21 μm is measured using the above-mentioned flow type particle image measuring device at 2 to 20 thousand particles/μl. By setting the concentration of the dispersion liquid to 12 to 20 thousand/μl, it is possible to maintain the particle concentration sufficient to maintain the accuracy of the apparatus even when the cut rate increases.

The outline of the measurement is described in the catalog of FPIA-1000 issued by Toa Medical Electronics Co., Ltd. (June 1995 version), the operating manual of the measuring device and JP-A-8-1364.
It is described in Japanese Patent No. 39, but is as follows.

The sample dispersion is passed through a flat and flat transparent flow cell (thickness of about 200 μm) (spreading along the flow direction). A strobe and a CCD camera are mounted on opposite sides of the flow cell so as to form an optical path that intersects and passes through the thickness of the flow cell. While the sample dispersion is flowing, strobe light is illuminated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Two
It is taken as a three-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. The circularity of each particle is calculated from the projected area of the two-dimensional image of each particle and the perimeter of the projected image using the above circularity calculation formula.

Further, the constitution of the toner preferable for achieving the object in the invention will be described in detail below.

Examples of the binder resin used in the present invention include vinyl resins, polyester resins and epoxy resins. Among them, vinyl resins and polyester resins are more preferable in terms of charging property and fixing property.

The vinyl resin monomer is styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene. , P-ethylstyrene, 2,4-dimethylstyrene,
such as pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene and pn-dodecyl styrene. Styrene derivative;
Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate, vinyl propionate , Vinyl esters such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
Dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
Α-Methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate , Acrylic acid esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone ,
Vinyl ketones such as vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes;
Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; α,
Examples include β-unsaturated acid esters and dibasic acid diesters. These vinyl-based monomers are used alone or 2
Used in more than one.

Among these, a combination of monomers that forms a styrene copolymer or a styrene-acrylic copolymer is preferable.

Further, it may be a polymer or copolymer which is cross-linked with a cross-linking monomer as exemplified below, if necessary.

Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate and 1,4-butanediol. Diacrylate, 1,5-pentanediol diacrylate, 1,6
Hexane diol diacrylate, neopentyl glycol diacrylate, and those in which the acrylates of the above compounds are replaced by methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate and triethylene glycol. Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #40
0 diacrylate, polyethylene glycol #600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compounds with methacrylate; as diacrylate compounds linked by a chain containing an aromatic group and an ether bond. , Polyoxyethylene (2)-2,2-bis(4-hydroxyphenyl)propane diacrylate, polyoxyethylene (4)-2,2-bis(4-hydroxyphenyl)propane diacrylate and acrylates of the above compounds In this case, the polyester type diacrylates include trade name MANDA (Nippon Kayaku Co., Ltd.).

As the polyfunctional cross-linking agent, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and the acrylates of the above compounds are replaced by methacrylates; Examples include triallyl cyanurate and triallyl trimellitate.

These cross-linking agents are based on other monomer components 10
0.01 to 10 parts by mass (more preferably 0.03 to 5 parts by mass) can be used with respect to 0 parts by mass.

Of these crosslinkable monomers, those which are preferably used in the resin for toner from the viewpoints of fixing property and anti-offset property include aromatic divinyl compounds (particularly divinylbenzene), chains containing an aromatic group and an ether bond. Examples of the diacrylate compound bonded by

In the present invention, polyurethane, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin may be added to the above-mentioned binder resin, if necessary. It can be mixed and used.

When two or more kinds of resins are mixed and used as a binder resin, as a more preferable form, it is preferable to mix resins having different molecular weights in an appropriate ratio.

The glass transition temperature of the binder resin is preferably 4
5 to 80° C., more preferably 55 to 70° C., the number average molecular weight (Mn) is 2,500 to 50,000, and the weight average molecular weight (Mw) is 10,000 to 1,000,000.
Is preferred.

As a method for synthesizing the vinyl polymer or the vinyl copolymer, a polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method can be used. When a carboxylic acid monomer or an acid anhydride monomer is used, it is preferable to use a bulk polymerization method or a solution polymerization method in view of the nature of the monomer.

The following method can be given as an example.
A vinyl copolymer can be obtained by a bulk polymerization method or a solution polymerization method using a monomer such as a dicarboxylic acid, a dicarboxylic acid anhydride or a dicarboxylic acid monoester. In the solution polymerization method, it is possible to partially dehydrate the dicarboxylic acid and dicarboxylic acid monoester units by devising the distillation conditions when the solvent is distilled off. Further, the vinyl-based copolymer obtained by the bulk polymerization method or the solution polymerization method is further heat-treated to further dehydrate it. It is also possible to partially esterify the acid anhydride with a compound such as an alcohol.

On the contrary, the vinyl copolymer thus obtained can be hydrolyzed to cyclize the acid anhydride group to partially convert it into a dicarboxylic acid.

On the other hand, using a dicarboxylic acid monoester monomer, a vinyl-based copolymer obtained by a suspension polymerization method or an emulsion polymerization method is dehydrated from the anhydride by dehydration by heat treatment and ring opening by hydrolysis treatment. Obtainable. The vinyl copolymer obtained by the bulk polymerization method or the solution polymerization method is dissolved in a monomer, and then by a suspension polymerization method or an emulsion polymerization method, a method of obtaining a vinyl polymer or a copolymer is used, A part of the acid anhydride can be ring-opened to obtain a dicarboxylic acid unit. Other resins may be mixed in the monomer during the polymerization, and the obtained resin can be subjected to an acid anhydride treatment by a heat treatment, or an esterification can be performed by a ring-opening alcohol treatment of the acid anhydride by a weak alkaline water treatment.

Since the dicarboxylic acid and dicarboxylic acid anhydride monomers have strong alternating polymerizability, the following method is preferable in order to obtain a vinyl copolymer in which functional groups such as anhydride and dicarboxylic acid are randomly dispersed. one of. This is a method in which a vinyl-based copolymer is obtained by a solution polymerization method using a dicarboxylic acid monoester monomer, the vinyl-based copolymer is dissolved in the monomer, and a binder resin is obtained by a suspension polymerization method. In this method, when distilling off the solvent after the solution polymerization, all or the dicarboxylic acid monoester portion can be dealcoholized and ring-closed and dehydrated depending on the treatment conditions to obtain an acid anhydride. During suspension polymerization, the acid anhydride group undergoes ring-opening by hydrolysis to give a dicarboxylic acid.

In the acid anhydride formation in the polymer, the infrared absorption of carbonyl shifts to the higher wave number side than that of the acid or ester, so that the production or disappearance of the acid anhydride can be confirmed.

In the binder resin thus obtained, the carboxyl group, the anhydride group and the dicarboxylic acid group are uniformly dispersed in the binder resin, so that the toner can be imparted with good chargeability.

The following polyester resins are also preferable as the binder resin.

The polyester resin is 45 to 55 in all components.
mol% is alcohol component, 55-45 mol%
Is the acid component.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl 1,3-hexanediol, hydrogenated bisphenol A, and a bisphenol derivative represented by the following formula (B);

[0096]

[Chemical 1]

Further, diols represented by the formula (C):

[0098]

[Chemical 2] Examples thereof include polyhydric alcohols such as glycerin, sorbit and sorbitan.

Examples of the divalent carboxylic acid containing 50 mol% or more in all the acid components include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides; succinic acid, adipic acid, sebacic acid, Alkyl dicarboxylic acids such as azelaic acid or anhydrides thereof, and succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or anhydrides thereof; fumaric acid, maleic acid, citraconic acid, itaconic acid Examples thereof include saturated dicarboxylic acids and anhydrides thereof. Examples of trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and anhydrides thereof.

The alcohol component of the particularly preferable polyester resin is a bisphenol derivative represented by the above formula (B), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenylsuccinic acid. Or an anhydride thereof, a dicarboxylic acid such as fumaric acid, maleic acid, or maleic anhydride; trimellitic acid or a tricarboxylic acid of an anhydride thereof.

This is because the heat roller fixing toner using the polyester resin obtained from these acid component and alcohol component as a binder resin has good fixability and excellent offset resistance.

The acid value of the polyester resin is preferably 90.
mgKOH/g or less, more preferably 50 mgKOH/g
g or less, OH value is preferably 50 mgKOH/g
The following is more preferable and 30 mgKOH/g or less is preferable. This is because as the number of terminal groups of the molecular chain increases, the charging characteristic of the toner becomes more environmentally dependent.

The glass transition temperature of the polyester resin is preferably 50 to 75° C., more preferably 55 to 65° C., and the number average molecular weight (Mn) is preferably 1,50.
0-50,000, more preferably 2,000-20,
It is 000. Weight average molecular weight of polyester resin (M
w) is preferably 6,000 to 100,000, and more preferably 10,000 to 90,000.

The sulfur-containing polymer or sulfur-containing copolymer used as the sulfur-containing compound used in the present invention is added mainly as a charge control agent. The sulfur-containing compound is preferably a polymer or copolymer containing a sulfonic acid group, and has a monomer unit having a sulfonic acid group. Examples of such a monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, methacryl sulfonic acid, and the following structure (1). A maleic acid amide derivative having
Examples thereof include a maleimide derivative having the following structure (2) and a styrene derivative having the following structure (3).

[0105]

[Chemical 3]

As the monomer for forming the copolymer with the sulfur-containing monomer, there is a vinyl-based polymerizable monomer,
A monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p- n-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy Styrene, styrene derivatives such as p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso
-Butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, 2-benzoyloxy Acrylic polymerizable monomers such as ethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate,
n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether,
Vinyl ether such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketone such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

As the polyfunctional polymerizable monomer, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxy diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane Tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis(4-(methacryloxydiethoxy)phenyl)propane, 2,
2'-bis(4-(methacryloxy-polyethoxyphenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like can be mentioned.

The method for producing the polymer includes bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, but solution polymerization is preferable from the viewpoint of operability and the like.

The counter ion of the sulfonic acid group-containing polymer is preferably a hydrogen ion, a sodium ion, a potassium ion, a calcium ion, or an ammonium ion, more preferably a hydrogen ion.

In the present invention, among the above-mentioned polymers having a sulfonic acid group, a copolymer of a styrene-based monomer, an acrylic-based monomer and a sulfonic acid-containing acrylamide monomer (containing a sulfonic acid group) is particularly preferable. A copolymer) is preferably used.

The styrene-based monomer and the acrylic-based monomer used in the sulfonic acid group-containing copolymer are appropriately selected from the vinyl-based monomers for producing the above-mentioned vinyl-based copolymer. Preferably, a combination of styrene and acrylic acid ester or styrene and methacrylic acid ester is used.

Examples of the sulfonic acid-containing acrylamide monomer used in the sulfonic acid group-containing copolymer include 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-n-hexanesulfonic acid. , 2-acrylamido-n-octanesulfonic acid, 2-acrylamido-n-dodecanesulfonic acid, 2-acrylamido-n-tetradecanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylphenyl Ethanesulfonic acid, 2-acrylamido-2-(4-chlorophenyl)propanesulfonic acid, 2-acrylamido-2-
Carboxymethylpropanesulfonic acid, 2-acrylamido-2-(2-pyridine)propanesulfonic acid, 2-
Acrylamide-1-methylpropanesulfonic acid, 3-
Examples thereof include acrylamide-3-methylbutane sulfonic acid, 2-methacrylamido-n-decane sulfonic acid, 2-methacrylamido-n-tetradecane sulfonic acid. Preferably, 2-acrylamido-2-methylpropanesulfonic acid is used.

The polymerization initiator used in synthesizing the sulfur-containing polymer or sulfur-containing copolymer is appropriately selected from the above-mentioned initiators used in producing the vinyl-based copolymer. It Peroxide initiators are preferably used.

The method for synthesizing the sulfur-containing polymer or sulfur-containing copolymer is not particularly limited, and any of solution polymerization, suspension polymerization and bulk polymerization can be used.
Solution polymerization in which copolymerization is performed in an organic solvent containing a lower alcohol is preferable.

The copolymerization mass ratio of the styrene-based monomer/acrylic monomer and the sulfonic acid-containing acrylamide-based monomer is as follows: styrene-based monomer/acrylic monomer:sulfonic acid-containing acrylamide-based monomer Body=98:2-80:2
It is preferably 0. When the proportion of the sulfonic acid-containing acrylamide monomer is less than 2% by mass, sufficient charging characteristics may not be obtained, which is not preferable.
If it is more than 0% by mass, environmental stability may become unstable, which is not preferable.

The acid value (mgKOH/g) of the sulfur-containing polymer or sulfur-containing copolymer is preferably 3 to 80. It is more preferably 5 to 40. More preferably, it is 10 to 30. When the acid value is less than 3, the charge control action is low and the environmental stability is low. When the acid value exceeds 80, it tends to be affected by moisture under high temperature and high humidity, and the environmental stability tends to be deteriorated.

The molecular weight of the sulfur-containing polymer or copolymer is such that the weight average molecular weight (Mw) is 2,000 to 200,000.
It may be 0, but is preferably 17,000 to 10
10,000, more preferably 27,000 to 5
It is 10,000. Weight average molecular weight (Mw) is 2,000
When it is less than 0, the sulfur-containing polymer or copolymer is compatible with the binder resin or is in a finely dispersed state, which makes it difficult to improve the charging characteristics and lowers the toner fluidity and transferability. Is not preferred. Further, the sulfur-containing polymer or copolymer has a weight average molecular weight (Mw) of 200,00.
If it exceeds 0, the sulfur-containing polymer or copolymer may be phase-separated from the binder resin and may be completely released from the toner particles, which may cause fog or environmental stability, which is not preferable.

The glass transition point (Tg) of the sulfur-containing polymer or copolymer is preferably 30°C to 120°C, more preferably 50°C to 100°C, further preferably 70°C to 95°C. is there. When the glass transition point (Tg) of the sulfur-containing polymer is less than 30° C., the fluidity and storage stability of the toner may be lowered, and the transferability may be poor, which is not preferable. When the glass transition point (Tg) exceeds 120° C., the fixing property may be deteriorated in the case of an image having a large toner printing rate, which is not preferable.

The volatile content of the sulfur-containing polymer or copolymer is 0.01% to 2.0% (more preferably 0.01% to 2.0%).
1% or less) is preferable. In order to reduce the volatile content to less than 0.01%, the volatile content removal process becomes complicated, and the volatile content is 2.
If it exceeds 0%, the electrification under high temperature and high humidity, especially the triboelectrification after standing is reduced. The volatile content of the polymer or copolymer decreases when heated at high temperature (135° C.) for 1 hour. It is the ratio of the mass.

The sulfur-containing polymer or copolymer "MEL
“T INDEX value” (MI value: g/10 min) is
0.1 to 200 is preferable. It is more preferably 0.2 to 150. If the MI value is less than 0.1, the compatibility of the polymer with the binder resin is lowered, so that the dispersibility in the toner particles is likely to be non-uniform, and the charge amount distribution of the toner is widened. When the MI value exceeds 200, the polymer or copolymer is too sharply melted, the blocking resistance is lowered, and the durability of many sheets is lowered. The MI value is measured according to the method A of JIS standard K7210. Then, the measured value is converted into a 10-minute value.

Extraction of the sulfur-containing polymer or copolymer from the toner is not particularly limited, and any method can be used.

(A) The "molecular weight and molecular weight distribution by GPC" of the sulfur-containing polymer or copolymer is measured by the following method.

The column was stabilized in a heat chamber at 40° C., and THF was added as a solvent to the column at this temperature.
(Tetrahydrofuran) at a flow rate of 1 ml/min, T
Inject about 100 μl of the HF sample solution for measurement. When measuring the molecular weight of a sample, calculate the molecular weight distribution
It is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for creating a calibration curve, for example,
The molecular weight of Tosoh or Showa Denko is 10 ² ~
It is suitable to use about 10 ⁷ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, Shodex GPC manufactured by Showa Denko KK
KF-801, 802, 803, 804, 805, 80
Combination of 6,807,800P and T manufactured by Tosoh Corporation
SKgel G1000H (H _XL ), G2000H (H
_XL ), G3000H (H _XL ), G4000H (H _XL ),
G5000H (H _XL ), G6000H (H _XL ), G70
00H (H _XL ), a combination of TSKguardcolumn.

The sample is manufactured as follows.

The sample is placed in tetrahydrofuran (THF), left to stand for several hours, shaken well and mixed well with THF (until the coalescence of the sample disappears), and left still for 12 hours or more. At this time, the leaving time in THF should be 24 hours or more. After that, a sample that has passed through a sample processing filter (pore size 0.45 to 0.5 μm, for example, Maisho Redisk H-25-5 manufactured by Tosoh Co., Ltd., Excicrodisk 25CR Gelman Science Japan Co., Ltd.) can be used. Use as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg/ml.

The "glass transition point" of the sulfur-containing polymer or copolymer (B) is determined by DSC measurement.

In the DSC measurement, it is preferable to use a highly accurate differential scanning calorimeter for the measurement principle. For example, DSC-7 manufactured by Perkin Elmer can be used.

The measuring method is ASTM D3418-82.
Carry out according to. For the measurement, a DSC curve measured when the temperature is raised at a temperature rate of 10° C./min after raising and lowering the temperature once to take a previous history is used.

The "acid value" of the sulfur-containing polymer or copolymer (C) is determined as follows. The basic operation is JIS-
According to K0070.

Free fatty acids contained in 1 g of sample,
Mg of potassium hydroxide required to neutralize resin acid, etc.
The number is called the acid value, and the test is conducted as follows.

(1) Reagent: (a) Solvent Ethyl ether-ethyl alcohol mixed solution (1
+1 or 2+1) or a benzene-ethyl alcohol mixture (1+1 or 2+1), and these solutions are neutralized with N/10 potassium hydroxide ethyl alcohol solution using phenolphthalein as an indicator immediately before use. (B) Phenolphthalein solution 1 g of phenolphthalein was added to 100 ml of ethyl alcohol (95 v/v%).
Dissolve in. (C) N/10 Potassium Hydroxide-Ethyl Alcohol Solution 7.0 g of potassium hydroxide is dissolved in as little water as possible, ethyl alcohol (95 v/v%) is added to make 1 liter, and the mixture is left for 2 to 3 days and then filtered. JIS K
Perform according to 8006 (basic items regarding titration during reagent content test).

(2) Operation: 1 to 20 g of a sample is accurately weighed, 100 ml of a solvent and a few drops of a phenolphthalein solution as an indicator are added thereto, and the sample is shaken sufficiently until it is completely dissolved. For solid samples, heat on a water bath to dissolve. After cooling, this was titrated with a N/10 potassium hydroxide ethyl alcohol solution, and the end point of neutralization was when the indicator was slightly reddish for 30 seconds.

(3) Calculation formula: The acid value is calculated by the following formula.

[0135]

[Equation 3] [A: acid value B: amount of N/10 potassium hydroxide ethyl alcohol solution used (ml) f: factor of N/10 potassium hydroxide ethyl alcohol solution S: sample (g)]

The "hydroxyl value" of the sulfur-containing polymer or copolymer (D) is determined as follows. The basic operation is JI
According to S=K0070.

The number of mg of potassium hydroxide required to neutralize acetic acid bound to a hydroxyl group when 1 g of a sample is acetylated by a prescribed method is called a hydroxyl value.
The test is performed according to the operation and the formula.

(1) Reagent: (a) Acetylating reagent 25 g of acetic anhydride was placed in 100 ml of a volumetric flask and pyridine was added to bring the total amount to 100 ml.
And shake well (in some cases, pyridine may be added). Keep the acetylating reagent away from moisture, carbon dioxide and acid vapors and store in amber bottles. (B) Phenolphthalein solution 1 g of phenolphthalein was added to 100 ml of ethyl alcohol (95 v/v%).
Dissolve in. (C) N/2 potassium hydroxide-ethyl alcohol solution
Dissolve 35 g of potassium hydroxide in as little water as possible,
Ethyl alcohol (95 v/v%) is added to make 1 liter, and the mixture is left standing for 2 to 3 days and then filtered. JIS K
8006.

(2) Operation: 0.5-2.0 g of a sample was accurately weighed in a round bottom flask, and the acetylation reagent 5 was added to it.
Correctly add ml. Place a small funnel on the neck of the flask and immerse about 1 cm bottom in a glycerin bath at 95-100° C. and heat. At this time, in order to prevent the temperature of the flask neck from rising due to the heat of the bath, cover the base of the neck of the flask with a cardboard disk with a round hole inside. After 1 hour, the flask was taken out of the bath, allowed to cool, 1 ml of water was added from the funnel and shaken to decompose acetic anhydride. To further complete the decomposition, the flask was again heated in the glycerin bath for 10 minutes, allowed to cool, the funnel and the flask wall were washed with 5 ml of ethyl alcohol, and phenolphthalein solution was used as an indicator for N/2 potassium hydroxide ethyl alcohol. Titrate with solution. A blank test will be conducted in parallel with the main test. In some cases, a KOH-THF solution may be used as the indicator.

(3) Calculation formula: The hydroxyl value is calculated by the following formula.

[0141]

[Equation 4] [A: hydroxyl value B: amount of N/2 potassium hydroxide ethyl alcohol solution used in blank test (ml) C: amount of N/2 potassium hydroxide ethyl alcohol solution used in this test (ml) f: N/2 Factor of potassium hydroxide ethyl alcohol solution S: sample (g) D: acid value]

The sulfur-containing polymer or copolymer can be used as it is, but it is preferable to pulverize it by a known pulverizing means so that the particle diameters are made uniform because the compatibility with other materials and the dispersibility are improved. The average particle size of the crushed particles is preferably 300 μm or less, more preferably 150 μm or less.
When it is less than μm, the dispersion with other materials becomes good,
Fog can be suppressed especially in terms of image quality.

The sulfur-containing polymer is preferably contained in an amount of 0.01 to 15 parts by mass per 100 parts by mass of the binder resin. The amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass.

The content of the polar group-containing monomer is 0.01
If it is less than 10 parts by mass, it is difficult to obtain a sufficient charge control action, and if it exceeds 15 parts by mass, the compatibility with other materials may decrease, or excessive charging may occur under low humidity, which is not preferable. ..

The content of the sulfur-containing polymer or copolymer in the toner can be measured by using a capillary electrophoresis method or the like.

Further, the toner of the present invention can be used in combination with other charge control agents, if necessary, in order to further stabilize the chargeability thereof. The charge control agent is used in an amount of 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the binder resin.

Examples of the charge control agent include the following.

Examples of the negative charge control agent for controlling the toner to have a negative charge include organic metal complexes and chelate compounds. Examples thereof include a monoazo metal complex, an aromatic hydroxycarboxylic acid metal complex, and an aromatic dicarboxylic acid metal complex. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides or esters thereof, or phenol derivatives of bisphenol.

As a positive charge control agent for controlling the toner to have a positive charge, a modified product of nigrosine with nigrosine and a fatty acid metal salt, tributylbenzylammonium-1-
Hydroxy-4-naphthosulfonate, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate; onium salts such as phosphonium salts thereof and chelate pigments thereof, such as triphenylmethane dyes and lake pigments thereof (lake forming agents). Examples thereof include phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid and ferrocyanine compounds); as metal salts of higher fatty acids, dibutyltin oxide, dioctyltin oxide, dicyclohexyltin. Examples thereof include diorganotin oxide such as oxide, dibutyltin borate, dioctyltin borate, and diorganotin borate such as dicyclohexyltin borate.

When the toner of the present invention is used as a magnetic toner, a magnetic substance is used as a colorant. The magnetic substance contained in the magnetic toner includes iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; metals such as Fe, Co, Ni, or these metals and Al, Co. , Cu, Pb, Mg, Ni, Sn,
Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, T
Alloys with metals such as i, W, V, and mixtures thereof.

Specifically, as the magnetic substance, iron tetraoxide is used.
(Fe₃O_Four), ferric sesquioxide (γ-Fe)₂O₃), iron oxide
Lead (ZnFe₂O_Four), yttrium iron oxide (Y₃Fe_FiveO
₁₂), iron cadmium oxide (CdFe₂O_Four), iron oxide gado
Rinium (Gd₃Fe_FiveO₁₂), iron oxide copper (CuFe
₂O_Four), iron oxide lead (PbFe)₁₂O₁₉), iron oxide nickel
(NiFe₂O_Four), iron neodymium oxide (NdFe)₂O₃),
Iron oxide barium (BaFe ₁₂O₁₉), iron oxide magnesium
Mu (MgFe₂O_Four), iron manganese oxide (MnFe
₂O_Four), lanthanum iron oxide (LaFeO₃), iron powder (F
e), cobalt powder (Co), nickel powder (Ni)
Be done. The above magnetic materials may be used alone or in combination of two or more.
Used together. A particularly suitable magnetic material is ferrosoferric oxide or
Is a fine powder of γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.05 to
At 2 μm, the magnetic characteristics under application of 795.8 kA/m are coercive force of 1.6 to 12.0 kA/m and saturation magnetization of 50 to 200 A.
m ² /kg (preferably 50 to 100 Am ² /kg) and residual magnetization of ^{2 to 20} Am ² /kg are preferable.

For 100 parts by mass of the binder resin, the magnetic material 1
It is preferable to use 0 to 200 parts by mass, preferably 20 to 150 parts by mass.

The non-magnetic colorant that can be used in the toner of the present invention includes any appropriate pigment or dye.
As the pigment, carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, red iron oxide,
There are phthalocyanine blue and indanthrene blue.
These are added in an amount of 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the binder resin. Examples of dyes include anthraquinone dyes, xanthene dyes, and methine dyes.
The amount added is ˜20 parts by mass, preferably 0.3 to 10 parts by mass.

In the present invention, one or more releasing agents are contained in the toner particles, if necessary. Examples of the release agent include the following.

Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax, and oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof. Waxes containing a fatty acid ester as a main component such as carnauba wax, sazol wax and montanic acid ester wax; and deoxidized fatty acid esters such as deoxidized carnauba wax. Further, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol, Saturated alcohols such as melicyl alcohol; long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide;
Saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N,N'-dioleyl Unsaturated fatty acid amides such as adipic acid amide and N,N-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N,N-distearyl isophthalic acid amide; calcium stearate, calcium laurate, Fatty acid metal salts (generally called metal soap) such as zinc stearate and magnesium stearate, and waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; Partial esterification products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride, and hydroxyl group-containing methyl ester compounds obtained by hydrogenation of vegetable oils and fats can be mentioned.

The amount of the releasing agent is 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin.

The mold releasing agent is usually prepared by dissolving a resin in a solvent, raising the temperature of the resin solution, and adding and mixing with stirring.
It can be contained in the binder resin by a method of mixing at the time of kneading.

A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added externally to the toner particles to increase the fluidity before and after the addition. For example, vinylidene fluoride fine powder, fluororesin powder such as polytetrafluoroethylene fine powder; wet process silica, fine powder silica such as dry process silica, fine powder titanium oxide, fine powder alumina, silane coupling agents thereof, There is a hydrophobic silica fine powder surface-treated with a titanium coupling agent and silicone oil.

The preferred fluidity improver is dry process silica fine powder or fumed silica fine powder produced by vapor phase oxidation of a silicon halogen compound. For example,
It utilizes the thermal decomposition and oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₄ +2H ₂ +O ₂ →SiO ₂ +4HCl

In this manufacturing process, it is possible to obtain a fine composite powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound. The average particle diameter of the particles is preferably in the range of 0.001 to 2 μm, and particularly preferably 0.0
It is preferable to use fine silica powder in the range of 02 to 0.2 μm.

Commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include, for example, those commercially available under the following trade names.

AEROSIL (Japan Aerosil Co., Ltd.) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N 20 V15 (WACK). -CHEMIE GMBH) N20E T30 T40 D-C Fine Silica (Dow Corning Co.) Francol (Fransil)

Furthermore, a hydrophobic silica fine powder obtained by subjecting a silica fine powder produced by vapor-phase oxidation of the silicon halogen compound to a hydrophobic treatment is more preferable. Among the hydrophobic silica fine powders, those obtained by treating the silica fine powder so that the degree of hydrophobicity measured by the methanol titration test is in the range of 30 to 80 are particularly preferable.

As a method of hydrophobizing, it is imparted by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs on silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.

Examples of the organosilicon compound are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Brommethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, one for each terminally located unit. Examples include dimethylpolysiloxane containing a hydroxyl group bonded to Si. Further, a silicone oil such as dimethyl silicone oil may be mentioned. These are used alone or as a mixture of two or more.

The fluidity improver has a specific surface area of 30 m ² /g or more, preferably 5 or more, as measured by the BET method by nitrogen adsorption.
0 m ² /g or more, more preferably 80 to 400 m ² /g
The ones give good results. The fluidity improver is 0.01 to 8 parts by mass, preferably 0.
It is preferable to use 1 to 4 parts by mass.

In the present invention, other inorganic fine powder may be externally added to the toner particles. Examples of the inorganic fine powder used in the present invention include compounds represented by the following formula. [M ₁ ]a[Ti]bOc (where M ₁ is Sr, M
represents a metal element selected from the group consisting of g, Zn, Co, Mn, Ca, Ba and Ce, a represents an integer of 1-9, b represents an integer of 1-9, and c represents 3-9. Indicates an integer. )

In particular, strontium titanate (SrTiO ₃ ) and calcium titanate (CaTiO ₃ ) are preferable because the effects of the present invention can be exhibited more effectively.

The inorganic fine particles used in the present invention are produced, for example, by a sintering method, mechanically pulverized, and then subjected to air classification,
It is preferable to use one having a desired particle size distribution.

The inorganic fine particles are used in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 8 parts by mass, based on 100 parts by mass of the toner particles.

If the addition amount is less than 0.1 parts by mass, it may not be possible to exhibit sufficient cleaning properties and polishing properties with respect to residual toner on the photoconductor and paper dust/ozone deposits. .. On the other hand, if the addition amount exceeds 10 parts by mass, fogging is likely to occur and the photoconductor may be scraped excessively, which is not preferable.

The inorganic fine particles used in the present invention have a weight average diameter of 0.2 to 4 μm, preferably 0.5 to 3 μm.

If the weight average diameter is less than 0.2 μm, a sufficient polishing effect may not be obtained, which is not preferable. If the weight average diameter exceeds 4 μm, fogging is likely to occur and the photoreceptor may be damaged, which is not preferable.

Hereinafter, a preferred method for producing the toner of the present invention will be specifically described with reference to the accompanying drawings.

1 and 2 are an example of a flow chart showing an outline of the toner manufacturing method. As shown in the flow chart, the toner manufacturing method is characterized in that the crushing step and the classifying step are performed in one pass without requiring the classifying step before the crushing treatment.

In the toner manufacturing method, a binder resin,
A mixture containing at least a colorant and a sulfur-containing compound is melt-kneaded, the obtained kneaded product is cooled, and then the crushed product is crushed by a crushing means to be used as a raw material for powder. Then, first, a rotor, which is a rotor having a predetermined amount of pulverized raw material attached to at least a central rotating shaft, and a stator arranged around the rotor with a certain distance from the rotor surface. By introducing into a mechanical crusher having an annular space formed by maintaining the gap and being in an airtight state, and rotating the rotor of the mechanical crusher at a high speed. Finely crush the object to be crushed. Next, the finely pulverized pulverized raw material is introduced into a classification step and classified to obtain a classified product which is a toner raw material composed of particles having a specified particle size. At this time, in the classification step, a multi-divided airflow classifier having at least a coarse powder region, a medium powder region and a fine powder region is preferably used as the classification means. For example, when a three-division airflow classifier is used, the powder raw material is classified into at least three types of fine powder, medium powder and coarse powder. In the classification process using such a classifier, coarse powder composed of particle groups having a particle size larger than the specified particle size and ultrafine powder composed of particle groups having a particle size smaller than the specified particle size are removed, and intermediate powder (toner particles) Is used as a toner after being mixed with the above inorganic fine powder and an external additive such as hydrophobic colloidal silica.

The ultrafine powder composed of the particles having a particle size smaller than the specified size, which has been classified in the classification step, is generally melted to produce a powder raw material made of the toner material introduced into the pulverization step. It is supplied to the kneading process and reused or discarded.

FIG. 3 and FIG. 4 show an example of an apparatus system applied to the toner manufacturing method of the present invention, and the present invention will be described more specifically based on this. As a powder raw material which is a toner raw material introduced into this apparatus system, a colored resin particle powder containing at least a binder resin, a colorant, and a sulfur-containing compound is used. A mixture obtained by melt-kneading a mixture of a resin, a colorant and a sulfur-containing compound, cooling the obtained kneaded product, and coarsely pulverizing the cooled product by a pulverizing means is used.

In this apparatus system, the pulverization raw material as the toner powder raw material is a mechanical pulverizer 301 which is a pulverizing means.
Then, a predetermined amount is introduced through the first fixed quantity feeder 315. The introduced pulverization raw material is instantaneously pulverized by the mechanical pulverizer 301 and is introduced into the second fixed amount feeder 2 (54 in FIG. 3) through the collecting cyclone 229 (53 in FIG. 3). Then, it is supplied into the multi-divided airflow classifier 1 (57 in FIG. 3) which is a classifying means through the vibrating feeder 3 (55 in FIG. 3) and further through the raw material supply nozzle 16 (148 in FIG. 3).

In this apparatus system, a predetermined amount introduced from the first fixed quantity feeder 315 to the mechanical crusher 301 which is the crushing means and a second fixed quantity feeder 2 (54 in FIG. 3) which is the classification means. Split airflow classifier 1 (5 in FIG. 3)
The relationship with the predetermined amount introduced in 7) is determined by the first fixed amount feeder 3
Where the predetermined amount introduced from 15 to the mechanical crusher 301 is 1, the place introduced from the second fixed amount feeder 2 (54 in FIG. 3) to the multi-split airflow classifier 1 (57 in FIG. 3). The quantification is preferably 0.7 to 1.7, more preferably 0.7.
˜1.5, and more preferably 1.0 to 1.2, from the viewpoint of toner productivity and production efficiency.

The airflow classifier is used by being connected to each other by a communication means such as a pipe and incorporated in an apparatus system. The integrated device system shown in FIG. 3 includes a multi-division classifier 57 (classification device shown in FIG. 8), a second constant quantity feeder 54, a vibrating feeder 55, a collection cyclone 59, a collection cyclone 60, and a collection cyclone 61. It is connected by a communication means. Further, the integrated device system shown in FIG. 4 has a multi-division classifying device 1 (classifying device shown in FIG. 9),
Quantitative feeder 2, vibrating feeder 3, collection cyclone 4,
The collection cyclone 5 and the collection cyclone 6 are connected by a communication means.

In this apparatus system, the powder is fed to the constant quantity feeder 2 by an appropriate means, and then introduced into the three-division classifier 1 through the vibrating feeder 3 and the raw material supply nozzle 16. Introducing 10-3
The powder is introduced into the three-division classifier 1 at a flow rate of 50 m/sec. Since the size of the classifying chamber of the three-division classifier 1 is usually [10 to 50 cm]×[10 to 50 cm], the powder is instantly divided into three or more kinds of particle groups within 0.1 to 0.01 seconds or less. Can be classified. Then, the three-division classifier 1 classifies the particles into large particles (coarse particles), intermediate particles, and small particles. After that, the large particles pass through the discharge conduit 11a and are sent to the collecting cyclone 6 and returned to the mechanical crusher 301. The intermediate particles are discharged to the outside of the system through the discharge conduit 12a, collected by the collecting cyclone 5 and collected as much as toner. The small particles are discharged to the outside of the system through the discharge conduit 13a, collected by the collecting cyclone 4, supplied to the melt-kneading step for producing the powder raw material made of the toner material, or reused. Be discarded. Collection cyclone 4,
5 and 6 can also function as suction decompression means for sucking and introducing the powder into the classification chamber through the raw material supply nozzle 16. Also, the large particles that are classified at this time are
It is preferable to re-introduce it into the first fixed amount feeder 315, mix it into the powder raw material, and pulverize it again with the mechanical pulverizer 301.

As shown in FIG. 3, the multi-split airflow classifier 5
The re-introduction amount of the large particles (coarse particles) re-introduced into the first fixed amount feeder 315 from 7 is 0 to 10.0 mass based on the weight of the finely pulverized product supplied from the second fixed amount feeder 54. %, and more preferably 0 to 5.0% by mass in terms of toner productivity. If the re-introduction amount of large particles (coarse particles) re-introduced from the multi-split air flow classifier 57 into the first fixed quantity feeder 315 exceeds 10.0 mass %, the mechanical crusher 3
In addition to increasing the dust concentration in 01 and increasing the load on the apparatus itself, it is not preferable from the viewpoint of toner productivity because the toner is over-crushed at the time of crushing and surface deterioration of the toner due to heat and fusion in the machine are likely to occur.

Further, as shown in FIG. 4, large particles (coarse particles) classified by the multi-split airflow classifier 1 are introduced into the third constant quantity feeder 331 and mechanically pulverized from the third constant quantity feeder 331. It is more preferable to introduce it into the machine 301 in terms of toner productivity. At this time, the re-introduction amount of the large particles (coarse particles) classified by the multi-split air flow classifier 1 is the same as that of the second constant quantity feeder 2
0 to 1 based on the weight of the finely pulverized product supplied from
From the standpoint of toner productivity, it is preferably 0.0% by mass, more preferably 0 to 5.0% by mass. When the re-introduction amount of large particles (coarse particles) re-introduced from the multi-split airflow classifier 1 to the third constant quantity feeder 331 exceeds 10.0 mass %, the coarse particles introduced into the mechanical crusher 301 The amount of particles to be re-introduced must be increased, and as a result, the dust concentration in the mechanical crusher 301 increases and the load on the device itself increases. It is not preferable from the viewpoint of toner productivity, because surface deterioration and in-machine fusion are likely to occur.

In this apparatus system, the particle size of the powder raw material is 95 to 100 mass% for 18 mesh pass (ASTME-11-61) and 100 mesh on (A
The STM E-11-61) is preferably 90 to 100% by mass.

In this apparatus system, the weight average particle diameter is 5.0 to 12.0 μm (further 5.0 to 10 μm).
m) to obtain a toner having a sharp particle size distribution, the weight average particle size of the finely pulverized product pulverized by a mechanical pulverizer is 5.0 to 12.0 μm, and 4.00 μm or less is 70.
Number% or less, more preferably 65 number% or less, 10.1 μm or more and 25 volume% or less, and further preferably 15 volume% or less.
As for the particle size of the classified intermediate powder, the weight average particle size of 5 to 12 μm, 4.00 μm or less is 40 number% or less, further 35 number% or less, 10.1 μm or more is 25 volume% or less, and further, It is preferably 15% by volume or less.

In the above-mentioned apparatus system applied to the toner manufacturing method of the present invention, the crushing step and the classifying step can be carried out in one pass without requiring the first classifying step before the crushing treatment.

The mechanical pulverizer preferably used as the pulverizing means used in the toner production method of the present invention will be described. Examples of the mechanical crusher include crusher inomizer manufactured by Hosokawa Micron Co., Ltd., Kawasaki Heavy Industries, Ltd.
Examples thereof include a crusher KTM and a turbo mill manufactured by Turbo Industry Co., Ltd. It is preferable to use these devices as they are or after appropriately improving them.

Among them, using a mechanical pulverizer as shown in FIGS. 5, 6 and 7 improves the efficiency because the pulverization process of the powder raw material can be easily performed.
preferable.

The mechanical crusher shown in FIGS. 5, 6 and 7 will be described below. FIG. 5 shows a schematic cross-sectional view of an example of a mechanical crusher, and FIG. 6 shows D- in FIG.
FIG. 7 shows a schematic cross-sectional view taken along the D′ plane, and FIG. 7 shows a perspective view of the rotor 314 shown in FIG. 5. The device is shown in FIG.
Casing 313, jacket 3 as shown in FIG.
16, a rotor 220 having a large number of grooves formed on a surface of a distributor 220, a casing 313, which is mounted on a central rotating shaft 312, and which rotates at high speed, and a constant interval is maintained on the outer circumference of the rotor 314. Stator 3 with a large number of grooves provided on the surface
10, a raw material inlet 31 for introducing a raw material to be treated
1. A raw material discharge port 302 for discharging the treated powder.

The crushing operation by the mechanical crusher configured as described above is performed, for example, as follows.

Powder inlet 31 of the mechanical grinder shown in FIG.
When a predetermined amount of the powder raw material is charged from No. 1, the particles are introduced into the pulverization processing chamber, and the rotor 314 having a large number of grooves formed on the surface which rotates at high speed in the pulverization processing chamber, and the surface thereof. The shock generated between the stator 310 having a large number of grooves and a large number of ultra-high speed vortices behind it, and the resulting high-frequency pressure vibrations cause instantaneous grinding. Then, the material is discharged through the raw material discharge port 302. The air (air) carrying the toner particles passes through the pulverization processing chamber, the raw material discharge port 302, the pipe 21.
9, the collecting cyclone 229, the bag filter 222, and the suction blower 224 are discharged to the outside of the system of the apparatus system. In the present invention, since the powder raw material is pulverized in this manner, the desired pulverization process can be easily performed without increasing the fine powder and the coarse powder.

Further, when crushing the crushed raw material by the mechanical crusher, it is preferable that the cold air is blown into the mechanical crusher together with the powder raw material by the cold air generating means 321. Furthermore,
The temperature of the cold air is preferably 0 to -18°C. Further, as the in-machine cooling means of the main body of the mechanical crusher, the mechanical crusher has a structure having a jacket structure 316,
It is preferable to pass cooling water (preferably antifreeze such as ethylene glycol). Further, the room temperature T1 in the swirl chamber 212 communicating with the powder introduction port in the mechanical crusher is 0° C. or lower, more preferably −5 to −15° C., and further preferably −7 by the above-mentioned cold air device and jacket structure. ~-12°C
Is preferable from the viewpoint of toner productivity. The room temperature T1 of the swirl chamber in the crusher is 0° C. or lower, more preferably −
By setting the temperature to 5 to -15°C, and more preferably to -7 to -12°C, it is possible to suppress surface alteration of the toner due to heat, and it is possible to efficiently pulverize the pulverization raw material. If the room temperature T1 of the vortex chamber in the pulverizer exceeds 0° C., the surface of the toner may be deteriorated by heat during pulverization and fusion in the machine is likely to occur, which is not preferable from the viewpoint of toner productivity. Further, when it is attempted to operate the room temperature T1 of the swirl chamber in the crusher at a temperature lower than −15° C., the refrigerant (alternative CFC) used in the cold air generating means 321 must be changed to CFC.

At present, the removal of CFCs is being promoted from the viewpoint of protecting the ozone layer. It is not preferable to use Freon as the refrigerant of the cold air generating means 321 from the viewpoint of environmental problems of the whole earth.

Alternative CFCs include R134A and R40
4A, R407C, R410A, R507A, R717
Among them, R404A is particularly preferable from the viewpoint of energy saving and safety.

Cooling water (preferably antifreeze such as ethylene glycol) is supplied to the inside of the jacket through the cooling water supply port 317 and discharged through the cooling water discharge port 318.

The finely pulverized material produced in the mechanical pulverizer is discharged from the powder outlet 302 through the rear chamber 320 of the mechanical pulverizer. At that time, the rear chamber 32 of the mechanical crusher
The room temperature T2 of 0 is preferably 30 to 60° C. from the viewpoint of toner productivity. By setting the room temperature T2 of the rear chamber 320 of the mechanical pulverizer to 30 to 60° C., it is possible to suppress surface alteration of the toner due to heat, and it is possible to efficiently pulverize the pulverization raw material. If the temperature T2 of the mechanical pulverizer is lower than 30° C., short pass may occur without pulverization, which is not preferable from the viewpoint of toner performance. On the other hand, if the temperature is higher than 60° C., the toner may be excessively pulverized during the pulverization, and the surface of the toner may be deteriorated by heat and fused inside the machine, which is not preferable from the viewpoint of toner productivity.

When crushing the crushed raw material with a mechanical crusher,
The temperature difference ΔT(T2-T1) between the room temperature T1 of the swirl chamber 212 and the room temperature T2 of the rear chamber 320 of the mechanical crusher is preferably 40 to 70°C, more preferably 42 to 67°C, and further preferably 45. From the viewpoint of toner productivity, it is preferable to set the temperature to 65°C. Mechanical crusher temperature T1 and temperature T
ΔT with 2 is 40 to 70° C., more preferably 42 to 67
C., more preferably 45 to 65.degree. C., the surface alteration of the toner due to heat can be suppressed, and the pulverization raw material can be efficiently pulverized. If the ΔT between the temperature T1 and the temperature T2 of the mechanical crusher is less than 40° C., there is a possibility that a short pass occurs without being crushed, which is not preferable from the viewpoint of toner performance. Also, if it is higher than 70°C, it may be over-crushed during crushing,
It is not preferable from the viewpoint of toner productivity, because the surface of the toner is likely to be deteriorated by heat and fusion in the machine is likely to occur.

When the pulverized raw material is pulverized by a mechanical pulverizer, the binder resin has a glass transition point (Tg) of 45 to 7
It is preferably 5°C, more preferably 55 to 65°C. Further, the room temperature T1 of the whirlpool chamber 212 of the mechanical crusher is
From the viewpoint of toner productivity, it is preferably 0° C. or less and 60 to 75° C. lower than Tg. The room temperature T1 of the swirl chamber 212 of the mechanical crusher is 0° C. or lower and Tg
By lowering the temperature by 60 to 75° C., the surface alteration of the toner due to heat can be suppressed, and the pulverization raw material can be efficiently pulverized. Also, the rear chamber 3 of the mechanical crusher
The room temperature T2 of 20 is 5 to 30° C. higher than Tg, and further,
It is preferably 10 to 20° C. lower. By lowering the room temperature T2 of the rear chamber 320 of the mechanical pulverizer to 5 to 30° C., more preferably 10 to 20° C. lower than Tg, it is possible to suppress the surface alteration of the toner due to heat, and efficiently pulverize the pulverized raw material. can do.

The peripheral speed of the tip of the rotating rotor 314 is preferably 80 to 180 m/sec, more preferably 90 to 170 m/sec, and further preferably 10 m/sec.
From the viewpoint of toner productivity, the range of 0 to 160 m/sec is preferable. The peripheral speed of the rotating rotor 314 is 80-
180 m/sec, more preferably 90 to 170 m/s
By setting ec, and more preferably 100 to 160 m/sec, it is possible to suppress insufficient pulverization or excessive pulverization of the toner, and it is possible to efficiently pulverize the pulverization raw material. When the peripheral speed of the rotor is lower than 80 m/sec, short pass is likely to occur without being pulverized, which is not preferable in terms of toner performance. The peripheral speed of the rotor 314 is 180 m/
If it is faster than sec, the load on the apparatus itself becomes large, and at the same time, the surface of the toner is over-crushed during the crushing and the surface of the toner is likely to be deteriorated or fused in the machine, which is not preferable from the viewpoint of toner productivity.

The minimum distance between the rotor 314 and the stator 310 is preferably 0.5-10.0 mm, more preferably 1.0-5.0 mm, and even more preferably 1.
It is preferably 0 to 3.0 mm. The distance between the rotor 314 and the stator 310 is 0.5 to 10.0 mm, more preferably 1.0 to 5.0 mm, and even more preferably 1.
By setting it to 0 to 3.0 mm, it is possible to suppress insufficient crushing of the toner and excessive crushing, and it is possible to efficiently crush the crushing raw material. If the distance between the rotor 314 and the stator 310 is larger than 10.0 mm, it is not preferable from the viewpoint of toner performance because short-pass easily occurs without being ground. When the distance between the rotor 314 and the stator 310 is smaller than 0.5 mm, the load on the apparatus itself increases, and at the same time, the surface of the toner is likely to be deteriorated due to heat and excessively pulverized during pulverization, or fusion in the machine is likely to occur. Therefore, it is not preferable in terms of toner productivity.

This crushing method does not require the first classification before the crushing step, has a simple structure, and does not require a large amount of air for crushing the crushing raw material. The amount of electricity consumed per 1 kg is
Compared with the case of manufacturing with the conventional collision type airflow crusher shown in FIG. 13, it is about 1/3 or less, and the energy cost can be kept low.

Next, the airflow classifier will be described.

As an example of a preferable multi-division airflow classifier, an apparatus of the type shown in FIG. 9 (cross-sectional view) will be illustrated as a specific example.

In FIG. 9, the side wall 22 and the G block 2 are shown.
3 forms part of the classification chamber, the classification edge blocks 24 and 25 being equipped with classification edges 17 and 18. The installation position of the G block 23 can be slid to the left and right. Further, the classification edges 17 and 18 have the shaft 17a.
It is rotatable about 18a and 18a, and the classification edge tip position can be changed by rotating the classification edge.
The classification edge blocks 24 and 25 can be slid to the left and right, and the knife edge type classification edges 17 and 18 are slid to the left and right accordingly. The classification area 30 of the classification chamber 32 is divided into three parts by the classification edges 17 and 18.

Raw material supply port 40 for introducing raw material powder
At the rear end of the raw material supply nozzle 16, a high pressure air supply nozzle 41 and a raw material powder introduction nozzle 42 at the rear end of the raw material supply nozzle 16, and a raw material supply having an opening in the classification chamber 32. The nozzle 16 is provided on the right side of the side wall 22, and the Coanda block 26 is installed so as to draw an elliptical arc in the extension direction of the lower tangent line of the raw material supply nozzle 16.
The left block 27 of the classifying chamber 32 is provided with a knife-edge type air inlet edge 19 in the right direction of the classifying chamber 32, and the left side of the classifying chamber 32 is provided with the air inlet pipes 14 and 15 that open into the classifying chamber 32. There is. In addition, as shown in FIG.
4 and 15 are provided with a first gas introduction adjusting means 20 and a second gas introduction adjusting means 21, such as a damper, a static pressure gauge 28 and a static pressure gauge 29.

The positions of the classification edges 17 and 18, the G block 23 and the air intake edge 19 are adjusted depending on the kind of the toner as the raw material to be classified and the desired particle size.

On the upper surface of the classifying chamber 32, there are discharge ports 11, 12 and 13 which open into the classifying chamber corresponding to the respective fractionation areas, and the discharge ports 11, 12 and 13 are connected to each other by a communicating means such as a pipe. Are connected to each other, and opening/closing means such as valve means may be provided in each.

The raw material supply nozzle 16 comprises a right-angled cylinder portion and a pyramidal cylinder portion, and the ratio of the inner diameter of the right-angled cylinder portion to the narrowest part of the pyramidal cylinder portion is 20:1 to 1:1 and preferably 10. :1
To 2:1 gives good introduction rates.

The classification operation in the multi-division classification area configured as described above is performed, for example, as follows. Outlet 1
A raw material supply nozzle 16 that reduces the pressure in the classification chamber through at least one of 1, 12 and 13 and has an opening in the classification chamber.
The powder is jetted into the classifying chamber through the raw material supply nozzle 16 at a speed of preferably 10 to 350 m/sec due to the ejector effect of the compressed air jetted from the high-pressure air supply nozzle 41 and the airflow flowing inside by the reduced pressure. And then disperse.

The particles in the powder introduced into the classification chamber move in a curved line by the action of the Coanda effect of the Coanda block 26 and the action of gas such as inflowing air at that time to move along the curved line. Depending on the particle size and the magnitude of inertial force, large particles (coarse particles) are outside the air stream, that is, the first fraction outside the classification edge 18, and intermediate particles are the second fraction between the classification edges 18 and 17. The small particles are classified into the third fraction inside the classification edge 17, the classified large particles are discharged from the discharge port 11, the classified intermediate particles are discharged from the discharge port 12, and the classified small particles. Are discharged from the discharge ports 13, respectively.

In the above-mentioned classification of the powder, the classification point is mainly determined by the edge tip positions of the classification edges 17 and 18 with respect to the lower end portion of the Coanda block 26 where the powder jumps out into the classification chamber 32. Further, the classification point is affected by the suction flow rate of the classification air flow, the ejection speed of the powder from the raw material supply nozzle 16, and the like.

Further, in the multi-split air stream classifier of the type shown in FIG. 9, a raw material supply nozzle, a raw material powder introduction nozzle and a high pressure air supply nozzle are provided on the upper surface of the multi-split air stream classifier, and the classification edge Since the position of the classification edge block having the above can be changed so that the shape of the classification area can be changed, the classification accuracy can be dramatically improved as compared with the conventional airflow type classification device.

Next, a method of measuring various physical property data measured in the following examples will be described below.

(1) Measurement of particle size distribution The particle size distribution can be measured by various methods, but in the present invention, it was measured using a Coulter counter multisizer.

As a measuring device, a Multisizer II type Coulter Counter (manufactured by Coulter) was used, and an interface (manufactured by Nikkaki) for outputting number distribution and volume distribution and a CX-1 personal computer (manufactured by Canon) were connected, As the electrolytic solution, a 1% NaCl aqueous solution is prepared using special grade or primary sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) as a dispersant is added to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 measuring samples are further added.
Add mg. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and as an aperture by the Multisizer II type Coulter Counter,
A 100 μm aperture is used when measuring the toner particle size. When measuring the particle size of the inorganic fine powder, a 13 μm aperture is used. The volume and number of the toner and the inorganic fine powder were measured, and the volume distribution and the number distribution were calculated. Then, the weight-based weight average diameter obtained from the volume distribution is obtained.

(2) Measurement of glass transition temperature (Tg) of toner and toner particles ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device), DSC-7 (manufactured by Perkin Elmer Co., Ltd.)
Measure according to 2.

The measurement sample is 5 to 20 mg, preferably 10
Precisely weigh mg. This is placed in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10° C./min at a measurement temperature range of 30 to 200° C. under normal temperature and normal humidity. During this temperature raising process, the temperature of 40 to 10
The endothermic peak of the main peak in the range of 0°C is obtained. The glass transition temperature Tg is defined as the intersection between the line at the midpoint of the baseline before and after the appearance of the endothermic peak and the differential heat curve.

(3) Measurement of molecular weight distribution of binder resin raw material The molecular weight of the chromatogram by GPC is measured under the following conditions.

The column is stabilized in a heat chamber at 40° C., and tetrahydrofuran (THF) as a solvent is passed through the column at this temperature at a flow rate of 1 ml/min.
Dissolve the sample in THF and filter with a 0.2 μm filter,
The filtrate is used as a sample. 0.05 as sample concentration
50% of the THF sample solution of the resin adjusted to
Inject ~200 μl and measure. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure
Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. having a molecular weight of 6×10 ² , 2.1×10 ³ , 4×10.
³ , 1.75×10 ⁴ , 5.1×10 ⁴ , 1.1×10 ⁵ ,
3.9×10 ⁵ , 8.6×10 ⁵ , 2×10 ⁶ , 4.48
It is suitable to use a standard polystyrene sample of at least about 10 points using a sample of ×10 ⁶ . R for the detector
An I (refractive index) detector is used.

As the column, a plurality of commercially available polystyrene gel columns are preferably combined in order to accurately measure the molecular weight region of 10 ³ to 2×10 ⁶ , for example, Water.
s Co., Ltd. of μ-styragel 500,10 ^3, 1
Combination of 0 ⁴ , 10 ⁵ and shodex manufactured by Showa Denko KK
KA-801, 802, 803, 804, 805, 80
A combination of 6,807 is preferred.

Next, FIG. 2 shows an example of the image forming method of the present invention.
A description will be given with reference to 0.

The surface of the photosensitive drum 701 is negatively charged by the contact charging means 742, which is a primary charger, and a digital latent image is formed by image scanning by exposure 705 by laser light, and the magnetic blade 711 and the magnet are included. The latent image is reversely developed with the dry magnetic toner (one-component magnetic developer) 710 of the developing device 709 having the developing sleeve 704. In the developing section, the conductive substrate of the photosensitive drum 701 is grounded, and the developing sleeve 704 is applied with an alternate bias, a pulse bias and/or a DC bias by the bias applying means 712. When the transfer paper P is conveyed and reaches the transfer portion, the contact transfer means 702 charges the transfer paper P from the back surface (the surface opposite to the photosensitive drum side) by the voltage application means 723, and the toner on the surface of the photosensitive drum 701 is charged. The image is transferred onto the transfer paper P by the contact transfer means 702.
Transferred to the top. The transfer paper P separated from the photosensitive drum 701 is subjected to a fixing process by a heating and pressure roller fixing device 707 in order to fix the toner image on the transfer paper P. The toner image may be transferred from the photosensitive drum 701 to the transfer paper P via the intermediate transfer body, or may be transferred to the transfer paper P without the intermediate transfer body.

The dry magnetic toner remaining on the photosensitive drum 701 after the transfer step is removed by the cleaning means 708 having a cleaning blade. If the amount of the dry magnetic toner remaining is small, it is possible to omit the cleaning step. The photosensitive drum 701 after cleaning is destaticized by the erase exposure 706, and again the contact charging means 74.
The process starting from the charging process by 2 is repeated.

The photosensitive drum 701 (that is, the electrostatic image carrier) has a photosensitive layer and a conductive substrate, and moves in the arrow direction. Non-magnetic cylindrical developing sleeve 70 which is a toner carrier
4 rotates in the developing unit so as to move in the same direction as the surface of the photosensitive drum 701. Inside the developing sleeve 704, a multi-pole permanent magnet (magnet roll) which is a magnetic field generating means is arranged so as not to rotate. The insulating dry magnetic toner 710 in the developing device 709 is applied on the non-magnetic cylindrical surface, and the magnetic toner is given a negative triboelectric charge by friction between the surface of the developing sleeve 704 and the magnetic toner. Further, a magnetic doctor blade 711 made of iron is placed close to the surface of the cylinder (interval 50 μm to 500 μm).
The magnetic toner layer is thin (30 μm) by arranging it so as to face one magnetic pole position of the multi-pole permanent magnet.
.About.300 μm) and regulated uniformly to form a magnetic toner layer thinner than the gap between the photosensitive drum 701 and the developing sleeve 704 in the developing section. By adjusting the rotation speed of the developing sleeve 704, the surface speed of the sleeve is made substantially equal to or close to the speed of the surface of the photosensitive drum. Instead of iron as the magnetic doctor blade 711, a permanent magnet may be used to form the opposing magnetic poles. An AC bias or a pulse bias may be applied to the developing sleeve 704 in the developing section by the bias means 712. This AC bias has an f of 200 to 4,000.
It is sufficient that 0 Hz and Vpp are 500 to 3,000 V.

When transferring the magnetic toner in the developing section,
The magnetic toner particles are transferred to the electrostatic image side by the action of the electrostatic force on the surface of the photosensitive drum and the AC bias or the pulse bias.

Instead of the magnetic doctor blade 711,
The magnetic toner may be applied onto the developing sleeve by regulating the layer thickness of the magnetic toner layer by pressing with an elastic blade formed of an elastic material such as silicone rubber.

FIG. 21 shows a specific example of the process cartridge of the present invention. The process cartridge is a cartridge in which the developing unit and the electrostatic image carrier are at least integrally formed, and the process cartridge is formed so as to be attachable to and detachable from the image forming apparatus main body (for example, a copying machine or a laser beam printer).

In FIG. 21, there is shown a process cartridge 750 in which a developing means 709, a drum-shaped electrostatic image carrier (photosensitive drum) 701, a cleaner 708 having a cleaning blade 708a, and a temporary charger (charging roller) 742 are integrated. It is illustrated.

In FIG. 21, the developing means 709 has an elastic blade 711a and a magnetic toner 710 in a toner container 760, and the magnetic toner 710 is used. At the time of development, the photosensitive drum 701 and the developing sleeve are biased by a bias from a bias applying means. The distance between the photosensitive drum 701 and the developing sleeve 704 is very important so that a predetermined electric field is formed between the photosensitive drum 704 and 704 and the developing process is appropriately performed.

[0233]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention.

Production Example 1 of Sulfur-Containing Copolymer 1 Methanol 300 parts by mass Toluene 100 parts by mass Styrene 480 parts by mass 2-Ethylhexyl acrylate 78 parts by mass 2-Acrylamido-2-methylpropanesulfonic acid 42 parts by mass 6 parts by mass of lauroyl peroxide The above raw materials were charged into a flask, equipped with a stirrer, a temperature measuring device, and a nitrogen introducing device, and solution polymerization was carried out at 70° C. under a nitrogen atmosphere to hold for 10 hours to complete the polymerization reaction.
The obtained polymer is dried under reduced pressure and coarsely pulverized to obtain a weight average molecular weight (Mw) of 27,000 and a glass transition temperature (Tg) of 73.
A sulfur-containing copolymer (a) having an average particle diameter of 420 μm at ℃ was obtained. Table 1 shows the physical properties of the sulfur-containing copolymer (a).

Production Examples 2 and 3 of Sulfur-Containing Copolymer By changing the composition ratio of the monomers used in Production Example 1 of the sulfur-containing copolymer, the sulfur-containing copolymers (b) and ( c)
Got

Production Examples 4 and 5 of Sulfur-containing Copolymer (a) By pulverizing the sulfur-containing copolymer (a) using a speed mill having a 1 mm screen and a jet pulverizer, Table 1
Sulfur-containing copolymer (d) having an average particle size of 290 μm shown in
And a sulfur-containing copolymer (e) having an average particle diameter of 150 μm were obtained.

Production Example 6 of Sulfur-Containing Copolymer Methanol 300 parts by mass Toluene 100 parts by mass Styrene 468 parts by mass 2-Ethylhexyl acrylate 90 parts by mass 2-Acrylamido-2-methylpropanesulfonic acid 42 parts by mass Lauroyl peroxide 6 parts by mass In the same manner as in Production Example 1 except that the above raw materials were used, a sulfur-containing copolymer (f) having the physical properties shown in Table 1 was obtained. Table 1 shows the physical properties of the sulfur-containing copolymer (f).

Production Example 7 of Sulfur-Containing Copolymer 7 Methanol 300 parts by mass Toluene 100 parts by mass Styrene 470 parts by mass 2-Ethylhexyl acrylate 90 parts by mass 2-Acrylamido-2-methylpropanesulfonic acid 40 parts by mass Lauroyl peroxide 10 parts by mass The above raw materials were charged into a 2 liter flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, and solution polymerization was carried out at 65°C for 10 hours under stirring and nitrogen introduction, and the contents were removed from the flask. The product was taken out, dried under reduced pressure, and coarsely crushed with a hammer mill to obtain a sulfur-containing copolymer (g) having the physical properties shown in Table 1.

Production Example of Sulfur-Containing Copolymer 8 Methanol 100 parts by mass Toluene 300 parts by mass Styrene 470 parts by mass 2-Ethylhexyl acrylate 90 parts by mass 2-Acrylamido-2-methylpropanesulfonic acid 40 parts by mass Lauroyl peroxide 12 parts by mass In the same manner as in Production Example 6 except that the above raw materials were used, a sulfur-containing copolymer (h) having the physical properties shown in Table 1 was obtained.

Production Example 9 of Sulfur-Containing Copolymer • Methanol 300 parts by mass • Toluene 100 parts by mass • Styrene 550 parts by mass • 2-Acrylamido-2-methylpropanesulfonic acid 50 parts by mass • Lauroyl peroxide 12 parts by mass In the same manner as in Production Example 6 except that was used, a sulfur-containing copolymer (i) having the physical properties shown in Table 1 was obtained.

Production Example 10 of Sulfur-Containing Copolymer 10 Methanol 300 parts by mass Toluene 100 parts by mass 4-t-Butylstyrene 570 parts by mass Methacrylsulfonic acid 30 parts by mass Lauroyl peroxide 10 parts by mass The above raw materials are used. Otherwise in the same manner as in Production Example 1, a sulfur-containing copolymer (j) having the physical properties shown in Table 1 was obtained.

Production Example 11 of Sulfur-Containing Copolymer 11 Methanol 300 parts by mass Toluene 100 parts by mass Styrene 560 parts by mass 2-Acrylamido-2-methylpropanesulfonic acid 40 parts by mass Lauroyl peroxide 12 parts by mass In the same manner as in Production Example 6 except that was used, a sulfur-containing copolymer (k) having the physical properties shown in Table 1 was obtained.

Production Example of Sulfur-Containing Copolymer 12 -Styrene 510 parts by mass-n-butyl acrylate 66 parts by mass-methacrylsulfonic acid 24 parts by mass Using the above raw materials, without adding a polymerization solvent and a polymerization initiator, The temperature was raised to 120° C. and bulk polymerization was carried out for 8 hours. Then, 300 parts by mass of xylene is added and 110° C.
To 300 parts by mass of xylene in which 6 parts by mass of t-butylperoxy-2-ethylhexanoate are dissolved.
The mixture was dropped for a period of time and kept for 2 hours to complete the polymerization reaction. The obtained polymer was dried under reduced pressure and coarsely pulverized to obtain a sulfur-containing copolymer (l) having the physical properties shown in Table 1.

Production Example 13 of Sulfur-Containing Copolymer 13 Methanol 100 parts by mass 2-butanone 300 parts by mass Styrene 470 parts by mass 2-Ethylhexyl acrylate 90 parts by mass 2-Acrylamido-2-methylpropanesulfonic acid 40 parts by mass Parts: 2,2 azobis(2-methylbutyronitrile) 6 parts by mass Divinylbenzene 0.05 parts by mass In the same manner as in Production Example 1 except that the above raw materials were used, a sulfur-containing copolymer having the physical properties shown in Table 1. (M) was obtained.

[0245]

[Table 1]

Example 1 Binder resin (polyester resin): 100 parts by mass (Tg 60° C., acid value 20 mg KOH/g, hydroxyl value 30
mgKOH/g, molecular weight: Mp7000, Mn300
0, Mw 55000)-Magnetic iron oxide: 90 parts by mass (average particle diameter 0.20 μm, 795.8 kA/m characteristics in magnetic field Hc 9.2 kA/m, σs 82 Am ² /kg, σ
r11.5Am ² /kg) ・Sulfur-containing compound (a): 2 parts by mass ・Low molecular weight ethylene-propylene copolymer: 3 parts by mass The above materials were used in a Henschel mixer (FM-75 type, Mitsui Miike Kakoki Co., Ltd.). After mixing well, the temperature is 130℃
The kneading was performed using a twin-screw kneader (PCM-30 type, manufactured by Ikegai Tekko Co., Ltd.) set to. The obtained kneaded product is cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain powder raw material (A)
(Coarse pulverized product) was obtained.

The powder raw material (A) was pulverized and classified by the apparatus system shown in FIG. A turbo mill T-250 type manufactured by Turbo Kogyo Co., Ltd. is used as the mechanical crusher 301, the gap between the rotor 314 and the stator 310 shown in FIG. 5 is 1.5 mm, and the peripheral speed of the rotor 314 is 115 m/s. I drove.

In the present embodiment, the powder raw material made of the coarsely pulverized material was fed to the table-type first constant quantity feeder 315 at 20 kg/
It was supplied to the mechanical crusher 301 at a rate of h and crushed. The powder raw material pulverized by the mechanical pulverizer 301 is entrained by the air sucked from the exhaust fan 224 while being accompanied by the cyclone 2
It is collected at 29 and introduced into the second fixed quantity feeder 2.
At this time, the inlet temperature in the mechanical grinder was -10.
℃, outlet temperature is 46°C, ΔT between inlet temperature and outlet temperature is 5
It was 6°C. At this time, the finely pulverized product A obtained by pulverizing with the mechanical pulverizer 301 has a weight average diameter of 6.6 μm.
m, and the particle size distribution was 53% by number of particles having a particle size of 4.0 μm or less, and 5.4% by volume of particles having a particle size of 10.1 μm or more had a sharp particle size distribution.

Next, the finely pulverized product A obtained by pulverizing with the above mechanical pulverizer 301 is introduced into the second constant amount feeder 2, and the pulverized product A is oscillated through the vibrating feeder 3 and the raw material supply nozzle 16.
Airflow type classifier 1 having the configuration of FIG. 9 at a rate of 2 kg/h
Introduced. In the airflow classifier 1, the Coanda effect is utilized to classify into three types of particle sizes: coarse powder, medium powder and fine powder. When introducing into the airflow classifier 1, the outlet 1
A raw material supply nozzle 16 that reduces the pressure in the classification chamber through at least one of 1, 12 and 13 and has an opening in the classification chamber.
An air flow flowing through the inside by the decompression and compressed air jetted from the high pressure air supply nozzle 41 were used. The introduced finely pulverized product was classified into three types, that is, a coarse powder G, a medium powder A-1, and a fine powder in an instant of 0.1 seconds or less. Of the classified materials, the coarse powder G is collected by the collection cyclone 6 and then 1.0 kg/h is added to the mechanical crusher 301 described above.
Was introduced at a ratio of 1, and was again introduced into the pulverizing step.

Medium powder A-1 classified by the above classification process
The (magnetic toner particles) has a weight average particle diameter of 6.5 μm, contains 20.5% by number of particles having a particle diameter of 4.0 μm or less, and contains 3.8% by volume of particles having a particle diameter of 10.1 μm or more. It became a sharp particle size distribution.

At this time, the ratio (that is, classification yield) of the finally obtained amount of the intermediate powder (magnetic toner particles) to the total amount of the powder raw material charged was 82%.

With respect to 100 parts by mass of the intermediate powder A-1, 1 part of the hydrophobic silica fine powder (BET 300 m ² /g) was added.
2 parts by mass were externally added with a Henschel mixer to obtain an insulating negatively-chargeable magnetic toner (A).

The weight average particle diameter of the magnetic toner (A) is 6.5.
was μm. In addition, the magnetic toner (A) is FPIA 1
As a result of measurement at 000, the number of particles having a circularity a=0.900 or more was 95.7% by number, and the number of particles having a circularity a=0.950 or more was 78.4% by number. The particle concentration A before cutting particles of 3 μm or less (all particles) is 15209.7 number/μl, and the measured particle concentration B of 3 μm or more is 130.
It was 28.3 pieces/μl.

FIG. 14 shows a particle size distribution, circularity distribution and circle equivalent diameter graph measured by FPIA 1000.

Evaluation-1 330 g of the dry magnetic toner (A) was placed in the developing device of Canon NP6350 copier adopting the electrophotographic process of FIG. 20 and placed in a room temperature and humidity room (23° C./50%) overnight. (1
Leave for 2 hours or more). After measuring the mass of the developing unit, NP6
The developing device was installed at 350, and the developing sleeve was rotated for 3 minutes. At this time, the cleaner section and the waste toner collecting section in the main body are once removed beforehand and the mass is measured. Using a test chart with a print ratio of 6%, 500 sheets were printed and the transfer rate was evaluated. Transfer rate of magnetic toner (A) is 96
It became%.

The transfer rate was calculated by the following calculation formula.

[0257]

[Equation 5]

Evaluation-2 After measuring the above - mentioned transfer rate, the copying machine and the developing device were moved to a room temperature and low humidity chamber (23° C./5%), and the developing device was taken out of the machine and left for 3 days. The developing device was installed in NP6350, and the developing sleeve was rotated for 1 minute. Using a test chart with a printing ratio of 6%, 1000 sheets were printed, and the image quality was evaluated by the fog in the white area on the test chart. The evaluation level is shown below.

REFLECTM Reflection Measuring Device for Fog Measurement
Using ETER (Tokyo Denshoku Co., Ltd.), the reflectance of the white part of the above image and the unused paper is measured, and the difference between the two is taken as the fog. Unused paper reflectance-Reflectance of white area of image = fog% A: Fog less than 0.1% B: Fog 0.1% or more and less than 0.5% C: Fog 0.5% or more and less than 1.5% D : Fog 1.5% or more and less than 2.0% E: Fog 2.0% or more

Evaluation-3 Magnetic toner (A) was printed on 100,000 sheets in a room temperature and low humidity chamber (23°C/5%) using a Canon NP6085 copying machine, and the final image density (F) was determined. Measure. Remove the developing unit from the copier and leave it in a high temperature and high humidity chamber (32.5°C/8
5%) for 2 days. At this time, in order to prevent dew condensation of the developing device, the developing device is sealed with a vinyl bag when it is placed in a high temperature and high humidity chamber, and the temperature and humidity are controlled for 5 hours or more, and then opened. The developing device was taken out, the developing device was installed in NP6085, the developing sleeve was rotated for 1 minute, and then 10 sheets of images were printed. The average value of the image densities of 10 sheets was taken as the density (R) after standing.

The charging performance of the magnetic toner was evaluated by the image density before standing (F) and the image density after standing (R). The evaluation level is shown below. A: (F)-(R) value is less than 0.02 B: (F)-(R) value is 0.02 or more and less than 0.05 C: (F)-(R) value is 0. 05 or more and less than 0.10 D: (F)-(R) value is 0.10 or more and less than 0.15 E: (F)-(R) value is 0.15 or more

Table 6 shows the above evaluation results.

Example 2 Finely pulverized product A was obtained in the same manner as in Example 1 except that the airflow classifier used in Example 1 was changed to the type shown in FIG.
2. Medium powder A-2 (magnetic toner particles) was prepared from 2. At this time, the ratio of the amount of the finally obtained intermediate powder (magnetic toner particles) to the total amount of the powder raw material charged (that is, classification yield) was 78%.

The particle size of the intermediate powder A-2 is shown in Table 3.

Examples 3 to 6 Medium powders A-3 and A- were prepared in the same manner as in Example 1 except that the conditions of pulverization and classification of the powder raw material (A) were changed by the apparatus system shown in FIG. 4, A-5 and A-6 (magnetic toner particles) were produced.

The particle sizes of the fine powders A3, A4, A5 and A6 and the medium powders A-3, A-4, A-5 and A-6 are shown in Tables 2 to 3. Table 5 shows the operating conditions of the apparatus at this time.

With respect to 100 parts by mass of the intermediate powder A-3, a hydrophobic silica fine powder (BET specific surface area 300 m ² /
g) 1.0 part by mass of medium powder A-4 and A-6 100
Hydrophobic silica fine powder (BET 300 m ²
/G) 0.6 parts by mass, and 100 parts by mass of the intermediate powder A-5 to a hydrophobic silica fine powder (BET 300 m ² /g) 1.
The magnetic toners (B), (C), (D), and (E) were obtained by externally adding 2 parts by mass with a Henschel mixer.

Weight average particle diameter of the above magnetic toner, and FP
The circularity measured by IA 1000 is shown in Table 4.

Then, the same evaluations as in Example 1 were carried out, and Table 6
Got the result.

Examples 7 to 18 In the same manner as in Example 1 except that the types of the sulfur-containing copolymer were changed to (b) to (m) to prepare the powder raw materials (B) to (M), respectively. Fine powders B to M and medium powders B-1 to M-1 (magnetic toner particles) were prepared, and hydrophobic silica fine powder was externally added to obtain magnetic toners (F) to (Q).

Weight average particle diameter of the above magnetic toner, and FP
The circularity measured by IA 1000 is shown in Table 4.

Fine powders B to M and medium powder B-1 to B-1 at this time
The particle sizes of M-1 are shown in Tables 2 to 3. Table 5 shows the operating conditions of the apparatus at this time.

Then, the same evaluations as in Example 1 were carried out, and Table 6
Got the result.

Comparative Example 1 The powder raw material (A) was pulverized and classified by the apparatus system shown in FIG. However, the collision type airflow crusher 58 is shown in FIG.
Using the crusher shown in FIG.
2) uses the structure of FIG. 12, and uses the second classification means (FIG. 1).
In 57, 57) has the structure shown in FIG.

In FIG. 12, 401 represents a cylindrical main body casing, 402 represents a lower casing, and a hopper 403 for discharging coarse powder is connected to the lower portion thereof. A classifying chamber 404 is formed inside the main body casing 401, and is closed by an annular guide chamber 405 attached to the upper part of the classifying chamber 404 and a conical (umbrella) upper cover 406 whose central portion is higher. There is.

A plurality of louvers 407 arranged in the circumferential direction are provided on the partition wall between the classification chamber 404 and the guide chamber 405, and the powder material and air sent into the guide chamber 405 are separated from each louver 407 by the classification chamber. Swirl to 404 for inflow.

The upper portion of the guide chamber 405 comprises a space between the conical upper casing 413 and the conical upper cover 406.

A classification louver 409 arranged in the circumferential direction is provided in the lower portion of the main body casing 401, and classification air for generating a swirling flow from the outside to the classification chamber 404 is classified by the louver 4.
It is introduced through 09.

At the bottom of the classifying chamber 404, a conical (umbrella) classifying plate 410 having a high central portion is provided.
A coarse powder outlet 411 is formed around the outer periphery of the. Further, a fine powder discharge chute 412 is connected to the center of the classifying plate 410,
The lower end of the chute 412 is bent into an L shape, and the bent end is located outside the side wall of the lower casing 402. Further, the chute is connected to a suction fan via a fine powder collecting means such as a cyclone or a dust collector, and the suction fan causes a suction force to act on the classification chamber 404 so that the chute flows into the classification chamber 404 from between the louvers 409. The swirling flow required for classification is generated by the suction air.

In this comparative example, the air classifier having the above structure was used as the first classifying means, but the air containing the above-mentioned coarsely pulverized product for toner production was supplied from the supply cylinder 408 into the guide chamber 405. Then, the air containing the coarsely crushed material passes from the guide chamber 405 between the louvers 407 and passes through the classification chamber 404.
While swirling, it flows in while being dispersed with a uniform concentration.

The coarsely crushed material which has swirled into the classifying chamber 404 swirls along with the suction air flow flowing from between the classification louvers 409 at the lower part of the classifying chamber, which is caused by the suction fan connected to the fine powder discharge chute 412. The centrifugal force acting on each particle centrifuges into coarse powder and fine powder, and the coarse powder swirling around the outer periphery of the classification chamber 404 is discharged from the coarse powder discharge port 411 and discharged from the lower hopper 403. It

The fine powder that moves to the central portion along the upper inclined surface of the classifying plate 410 is discharged by the fine powder discharging chute 412.

The pulverized raw material was supplied to the air flow classifier shown in FIG. 12 through the supply pipe 408 by the injection feeder 135 at a rate of 10.0 kg/h by the table-type first constant-volume feeder 121 and the particles were supplied. The particles were classified by centrifugal separation due to the centrifugal force acting on. The classified coarse powder is supplied through the coarse powder discharge hopper 403 from the pulverized material supply port 165 of the collision type air flow pulverizer shown in FIG. 13, and the pressure is 0.588.
MPa (6.0 kg/cm ² ) (G), 6.0 Nm ³ /m
After being crushed by using compressed air of in, it was circulated through the airflow classifier again while being mixed with the toner crushing raw material supplied in the raw material introducing section, and closed circuit pulverization was performed. on the other hand,
The classified fine powder was collected by the cyclone 131 while being entrained by the suction air from the exhaust fan.

At this time, the finely pulverized product N had a weight average diameter of 6.
The particle size distribution was 7 μm, 63.3% by number of particles having a particle size of 4.0 μm or less, and 11.1% by volume of particles having a particle size of 10.1 μm or more.

The finely pulverized product N thus obtained is passed through the second constant quantity feeder 124 and the vibrating feeder 125 and the nozzle 1.
In order to classify into 3 types of coarse powder, medium powder N-1 and fine powder by utilizing the Coanda effect at a rate of 13.0 kg/h via 48 and 149, an air flow type classifier shown in FIG. Introduced. At the time of introduction, outlets 158, 159 and 16
Collection cyclones 129, 130 and 1 in communication with 0
The suction force derived from the reduced pressure in the system due to the reduced suction pressure of 31 was used. Of the classified materials, the coarse powder was collected by the collection cyclone 129, and then introduced into the collision-type airflow pulverizer 58 described above at a rate of 1.0 kg/h and again introduced into the pulverization step.

Medium powder N-1 classified in the above classification step
Had a particle size distribution in which the weight average particle size was 6.6 μm, the particles having a particle size of 4.0 μm or less were 23.3% by number, and the particles having a particle size of 10.1 μm or more were 5.1% by volume.

At this time, the ratio of the amount of the intermediate powder finally obtained to the total amount of the powdered raw materials charged (that is, the classification yield) was 69%.

With respect to 100 parts by mass of this medium powder N-1, 1 part of hydrophobic silica fine powder (BET 300 m ² /g) was added.
2 parts by mass was externally added with a Henschel mixer to obtain a comparative magnetic toner (a).

The weight average particle diameter of the comparative magnetic toner (a) was 6.5 μm. Comparative magnetic toner (a) with FPIA
As a result of measurement at 1000, 94.0% by number of particles having a circularity a=0.900 or more and 67.8% by number of particles having a circularity a=0.950 or more.

FIG. 15 shows a graph of particle size distribution, circularity distribution and circle equivalent diameter measured by FPIA 1000.

The same evaluations as in Example 1 were carried out and the results shown in Table 6 were obtained.

Comparative Example 2 Using the powder raw material (A), fine pulverization and classification were carried out by the apparatus system shown in FIG. As the collision type airflow crusher, the conventional one shown in FIG. 13 was used, and as the first classification means, the airflow classifier shown in FIG. 12 was used as in Comparative Example 1. As a result, the powder raw material was supplied at a rate of 8.0 kg/h, the weight average particle diameter was 5.9 μm, and the particle diameter was 4.0 μm.
The following particles are 72.3% by number, and the particle size is 10.1 μm.
A finely pulverized product O containing 8.0% by volume of the above particles was obtained.

Next, the obtained finely pulverized product was 10.0 kg/
At a rate of h, the particles were introduced into the airflow classifier having the configuration shown in FIG. Of the classified materials, the coarse powder was collected by the collection cyclone 129, and then introduced into the collision-type airflow pulverizer 58 described above at a rate of 1.0 kg/h and again introduced into the pulverization step.

Medium powder O-1 classified by the above classification process
Had a weight average particle size of 6.0 μm, particles having a particle size of 4.0 μm or less were 33.8% by number, and particles having a particle size of 10.1 μm or more were 4.1% by volume.

At this time, the ratio of the amount of the intermediate powder finally obtained to the total amount of the powder raw materials charged (that is, the classification yield) was 63%.

With respect to 100 parts by mass of the medium powder O-1, a hydrophobic silica fine powder (BET 300 m ² /g) of 1.
2 parts by mass were externally added with a Henschel mixer to obtain a comparative magnetic toner (b).

The comparative magnetic toner (b) was used as FPIA 100
The results measured at 0 are shown in Table 4.

The same evaluations as in Example 1 were carried out and the results shown in Table 6 were obtained.

Comparative Example 3 A powder raw material (P) was obtained in the same manner as in Example 1 except that the sulfur-containing copolymer (a) was changed to a monoazo metal complex (negative charge control agent). Using this powder raw material (P), Example 1
Fine pulverization and classification were performed with the same apparatus system as in. The particle sizes of the fine powder P and the medium powder P-1 are shown in Tables 2 to 3.
Table 5 shows the operating conditions of the apparatus at this time. At this time, the ratio of the amount of the medium powder finally obtained to the total amount of the powder raw materials charged (that is, classification yield) was 81%.

With respect to 100 parts by mass of the intermediate powder P-1, 1. hydrophobic silica fine powder (BET 300 m ² /g) was added.
2 parts by mass were externally added with a Henschel mixer to obtain a comparative magnetic toner (c).

Comparative magnetic toner (c) was treated with FPIA 100
The results measured at 0 are shown in Table 4.

Evaluations similar to those in Example 1 were carried out, and the results shown in Table 6 were obtained.

Comparative Example 4 Fine powder Q and intermediate powder Q-1 were obtained in the same manner as in Example 1 except that the powder raw material (P) produced in Comparative Example 3 was used.
The particle sizes of the fine powder Q and the medium powder Q-1 are shown in Tables 2 to 3. Table 5 shows the operating conditions of the apparatus at this time. Further, the ratio of the amount of the intermediate powder finally obtained to the total amount of the powder raw material charged at this time (that is, the classification yield) was 83%.

With respect to 100 parts by mass of the intermediate powder Q-1, a hydrophobic silica fine powder (BET 300 m ² /g) of 1.
2 parts by mass were externally added by a Henschel mixer to obtain a comparative magnetic toner (d).

Table 4 shows the weight average particle diameter of the comparative magnetic toner (d) and the result of measurement with FPIA 1000.

The same evaluations as in Example 1 were carried out and the results shown in Table 6 were obtained.

Examples 19 to 20 Medium powders A-7 and A- were prepared in the same manner as in Example 1 except that the conditions of pulverization and classification of the powder raw material (A) were changed by the apparatus system shown in FIG. 8 (classified product) was produced. Fine powder A
7 and A8 and the particle sizes of the medium powders A-7 and A-8 are shown in Tables 2 and 3.
Became. Table 5 shows the operating conditions of the apparatus at this time.

For 100 parts by mass of this intermediate powder A-7, 1. hydrophobic silica fine powder (BET 180 m ² /g) was added.
Hydrophobic silica fine powder (BET 180 m ² /g) 1. 5 parts by mass, and 100 parts by mass of the medium powder A-8.
Externally added 0 parts by mass of each in a Henschel mixer to obtain comparative magnetic toners (R) and (S).

Table 4 shows the weight average particle diameters of the magnetic toners (R) and (S), and the circularity measured by FPIA 1000.
Became.

Evaluations similar to those in Example 1 were carried out, and the results shown in Table 6 were obtained.

Comparative Example 5 Intermediate powder R-1 classified product was prepared in the same manner as in Example 1 except that the powder raw material (A) was used in the apparatus system shown in FIG. 11 except that the conditions for pulverization and classification were changed. Was produced. The particle sizes of the fine powder R1 and the medium powder R-1 are shown in Tables 2 and 3. Table 5 shows the operating conditions of the apparatus at this time.

With respect to 100 parts by mass of this intermediate powder R-1, 1. hydrophobic silica fine powder (BET 180 m ² /g) was added.
Externally added 5 parts by mass with a Henschel mixer to obtain a comparative magnetic toner (e).

Table 4 shows the weight average particle diameter of the comparative magnetic toner (e) and the circularity measured by FPIA 1000.

The same evaluations as in Example 1 were carried out and the results in Table 6 were obtained.

[0315]

[Table 2]

[0316]

[Table 3]

[0317]

[Table 4]

[0318]

[Table 5]

[0319]

[Table 6]

Production Example of Inorganic Fine Powder 1: Strontium Titanate
Fine strontium carbonate 600 g of strontium carbonate and 320 g of titanium oxide were wet mixed in a ball mill for 8 hours, filtered and dried, and the mixture was molded at a pressure of 0.49 MPa (5 kg/cm ² ) and temporarily stored at 1100° C. for 8 hours. Baked This was mechanically pulverized to obtain strontium titanate fine powder (M-1) having a weight average diameter of 2.0 μm.

Production Examples 2 to 3 of Inorganic Fine Powder: Stroke Titanate
Rontium fine powder The calcined product obtained in the same manner as in Production Example 1 above was changed in crushing and classification conditions to give a weight average diameter of 4.8 μm (M-
2) and strontium titanate fine powder having a weight average diameter of 0.3 μm (M-3) was obtained.

Production Example 4 of Inorganic Fine Powder: Calcium Titanate
505 g of finely powdered calcium carbonate and 400 g of titanium oxide were wet mixed in a ball mill for 8 hours, filtered and dried, and the mixture was molded at a pressure of 0.49 MPa (5 kg/cm ² ) and temporarily stored at 1100° C. for 8 hours. Baked This was mechanically pulverized to obtain calcium titanate fine powder (M-4) having a weight average diameter of 1.8 μm.

Example 21 10 of the intermediate powder A-1 (toner particles) obtained in Example 1
To 0 parts by mass, 1.0 part by mass of hydrophobic silica fine powder (BET specific surface area 300 m ^{2 /} g) and 4.0 parts by mass of strontium titanate (M-1) were externally added, and a magnetic toner (T ) Was prepared. Table 7 shows each characteristic.

Example 22 10 of the intermediate powder A-1 (toner particles) obtained in Example 1
To 0 parts by mass, 1.0 part by mass of hydrophobic silica fine powder (BET specific surface area 300 m ^{2 /} g) and 4.0 parts by mass of strontium titanate (M-2) were externally added, and a magnetic toner (U ) Was prepared. Table 7 shows each characteristic.

Example 23 10 of the intermediate powder A-1 (toner particles) obtained in Example 1
To 0 parts by mass, 1.0 part by mass of hydrophobic silica fine powder (BET specific surface area 300 m ^{2 /} g) and 4.0 parts by mass of strontium titanate (M-3) were externally added, and a magnetic toner (V ) Was prepared. Table 7 shows each characteristic.

Example 24 10 of the intermediate powder A-1 (toner particles) obtained in Example 1
To 0 parts by mass, 1.0 part by mass of hydrophobic silica fine powder (BET specific surface area 300 m ^{2 /} g) and 4.0 parts by mass of calcium titanate (M-4) were externally added, and a magnetic toner (N )
Was prepared. Table 7 shows each characteristic.

Comparative Example 6 10 of the intermediate powder N-1 (toner particles) obtained in Comparative Example 1
To 0 parts by mass, 1.0 part by mass of hydrophobic silica fine powder (BET specific surface area 300 m ^{2 /} g) and 4.0 parts by mass of strontium titanate (M-1) were externally added, and a comparative magnetic toner ( f) was prepared. Table 7 shows each characteristic.

Comparative Example 7 10 of the intermediate powder P-1 (toner particles) obtained in Comparative Example 3
To 0 parts by mass, 1.0 part by mass of hydrophobic silica fine powder (BET specific surface area 300 m ^{2 /} g) and 4.0 parts by mass of strontium titanate (M-1) were externally added, and a comparative magnetic toner ( g) was prepared. Table 7 shows each characteristic.

[0329]

[Table 7]

Using the magnetic toners (T), (U), (V) and (W) and the comparative magnetic toners (f) and (g) in the same manner as in Example 1, the transfer rate (%), fog and The charging performance was evaluated. Furthermore, the presence/absence of cleaning failure, the occurrence of drum scraping, and the image deletion were evaluated according to the following formula. The evaluation results are shown in Table 8.

Presence/absence of cleaning failure and drum scraping Canon's modified NP6085 copier (developing, drum, optics, paper conveying system, etc. were all adjusted to increase the copying speed by 20%). 1°C/5%)
Images were printed on 0,000 sheets, and the presence or absence of cleaning failure and the amount of drum abrasion were evaluated. At this time, the cleaning blade was brought into contact with the drum at a total pressure of 5.88 N (600 g).

Evaluation level of cleaning A: No defective cleaning occurred B: A small defective cleaning was confirmed on the white background. C: A defective cleaning can be clearly confirmed on the image.

Drum abrasion level A: abrasion amount less than 10.0Å B: abrasion amount 10.0Å to 25.0Å C: abrasion amount 25.0Å to 50.0Å D: abrasion amount 50.0Å to 150.0Å E : Abrasion amount 150.0Å or more

A high-temperature, high-humidity chamber (32.30%) was prepared by using a modified NP6085 modified copying machine manufactured by Canon (developing, drum, optics, paper conveying system, etc. were all adjusted to increase copying speed by 20%).
Images were printed on 500,000 sheets at 5° C./85%), and the presence or absence of image deletion was confirmed. At this time, the cleaning blade was brought into contact with the drum at a total pressure of 5.49 N (560 g).

[0335] - image level flow A: No spot image area B: less than spot image area 1 cm ² C: spot image area 1cm ² ~5cm ² D: spot image area 5cm ² ~10cm ² E: spot image area 10 cm ² or more

[0336]

[Table 8]

[0337]

As described above, according to the present invention, it is a toner that can reduce the amount of transfer residual toner, which is waste toner, and can maintain good developability with high transfer efficiency, thus obtaining a high quality image. be able to.

[Brief description of drawings]

FIG. 1 is a flowchart for explaining a toner manufacturing method of the present invention.

FIG. 2 is a flowchart for explaining a toner manufacturing method of the present invention.

FIG. 3 is a schematic view showing a specific example of an apparatus system for carrying out the toner manufacturing method of the present invention.

FIG. 4 is a schematic view showing a specific example of an apparatus system for carrying out the toner manufacturing method of the present invention.

FIG. 5 is a schematic sectional view of an example of a mechanical pulverizer used in the toner pulverizing step of the present invention.

FIG. 6 is a schematic cross-sectional view taken along the line DD′ in FIG.

FIG. 7 is a perspective view of the rotor shown in FIG.

FIG. 8 is a schematic cross-sectional view of a multi-split airflow classifier used in a toner classification step of the present invention.

FIG. 9 is a schematic cross-sectional view of a multi-division airflow type classification device preferably used in the toner classification step of the present invention.

FIG. 10 is a flowchart for explaining a conventional manufacturing method.

FIG. 11 is a system diagram showing a conventional manufacturing method.

FIG. 12 is a schematic cross-sectional view of an example of a classifier used in a conventional first classifying means or second classifying means.

FIG. 13 is a schematic sectional view of a conventional collision type airflow crusher.

FIG. 14 is a graph showing the particle size distribution, circularity distribution, and circle equivalent diameter of the intermediate powder A-1.

FIG. 15 is a graph showing the circularity distribution of medium powder A-1.

FIG. 16 is a graph showing the equivalent circle diameter of medium powder A-1.

FIG. 17 is a graph showing the particle size distribution of medium powder N-1.

FIG. 18 is a graph showing the circularity distribution of medium powder N-1.

FIG. 19 is a graph showing a circle equivalent diameter of a medium powder N-1.

FIG. 20 is a schematic explanatory diagram for explaining an example of the image forming method of the present invention.

FIG. 21 is a schematic explanatory view for explaining an example of the process cartridge of the present invention.

[Explanation of symbols]

1 Multi-division classifier 2 2nd fixed quantity feeder 3 Vibration feeder 4,5,6,229 Collection cyclone 11,12,13 Discharge port 11a,12a,13a Discharge conduit 14,15 Intake pipe 16 Raw material supply nozzle 17,19 , 117,118 Classification edge 19 Inlet edge 20 First gas introduction adjusting means 21 Second gas introduction adjusting means 22,23 Side wall 24,25 Classification edge block 26 Coanda block 27 Left block 28,29 Static pressure gauge 30 Classification area 32 Classification chamber 40 Raw material supply port 41 High pressure air supply nozzle 42 Raw material powder introduction nozzle 54 Second fixed quantity feeder 55 Vibratory feeder 57 Multi-division classifier 53,59,60,61 Collection cyclone 62,65 Injection feeder 63 Medium powder (Product) 64 Ultrafine powder 148,149 Raw material supply pipe 150 Upper wall of classification chamber 151 Air inlet edge 152,153 Air inlet pipe 154,155 Gas introduction control means 156,157 Static pressure gauge 158,159,160 Discharge port 212 Swirl chamber 219 pipe 220 distributor 222 bag filter 224 suction blower 229 collection cyclone 301 mechanical grinder 302 powder discharge port 310 stator 311 powder input port 312 rotary shaft 313 casing 314 rotor 315 first constant quantity supply machine 316 jacket 317 cooling Water supply port 318 Cooling water discharge port 320 Rear chamber 321 Cold air generating means 331 Third constant quantity feeder

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/08 G03G 9/08 365 365 4D067 365 15/02 101 9/083 102 9/087 15/08 504A 15 /02 101 15/09 A 102 15/16 15/08 504 103 15/09 9/08 346 15/16 381 103 101 (72) Inventor Masami Higashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Tsuneo Nakanishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tadashi Michigami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. ( 72) Inventor Neneko Shibayama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kazuya Kazuya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Katsuhisa Yamazaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Takeshi Naka, 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AA02 AA06 AA15 AB02 AB04 CA04 DA02 EA03 EA05 EA06 EA07 EA10 2H031 AA03 AA05 AC08 AC17 AC30 BA02 EA01 EA03 2H077 AA12 AD02 AD06 AD13 AD23 EA12 FA19 FA21 2H200 GA23 GA44 GA47 HA02 HA28 HB12 JA01 JB10 JB26 JC01 4D065 AA09 EB20 ED24 ED31 ED45 4D067 CG04 EE22 EE35 GA20 GB03 GB07

Claims (36)

[Claims] 1. A toner having at least a binder resin and a colorant, the toner containing a sulfur-containing compound selected from the group consisting of a sulfur-containing polymer and a sulfur-containing copolymer, and a weight average of the toner. Particles having a particle diameter of 5 to 12 μm and having a circularity a of 0.900 or more determined by the following formula (1) among particles of 3 μm or more of the toner have a number-based cumulative value of 90 number% or more, Circularity a=L ₀ /L (1) [In the formula, L ₀ represents the perimeter of a circle having the same projected area as the particle image, and L represents the perimeter of the particle image. And a) the relationship between the cut ratio Z and the toner weight average diameter X satisfies the following formula (2), and the cut ratio Z≦5.3×X (2) [where the cut ratio Z is manufactured by Toa Medical Electronics Co., Ltd. When the particle concentration A (number/μl) of all the measured particles measured by the flow type particle image analyzer FPIA-1000 and the measured particle concentration B (number/μl) with an equivalent circle diameter of 3 μm or more are given by the following formula (3): Indicated by. Z=(1−B/A)×100 (3)], and in particles of 3 μm or more of the toner, the circularity (a) of 0.950 or more in the number-based circularity distribution of the circularity (a). The relationship between the number-based cumulative value Y of the particles having the average particle size X and the toner weight average diameter X satisfies the following formula (4): The number-based cumulative value Y of the particles having a circularity of 0.950 or more Y≧exp5.51×X ^−0.645 ( 4) [However, the weight average particle diameter X of the toner is X: 5.0 to 12.0.
μm] or b) The relationship between the cut rate Z and the toner weight average diameter X satisfies the following formula (5), and the cut rate Z>5.3×X (5) and the toner particles having a diameter of 3 μm or more are circular. In the number-based circularity distribution of the degree (a), the relationship between the number-based cumulative value Y of the particles having the circularity (a) of 0.950 or more and the toner weight average diameter X satisfies the following expression (6). Toner. Number-based cumulative value of particles having a circularity of 0.950 or more Y≧exp 5.37×X ^−0.545 (6) [However, weight average particle diameter X of toner: 5.0 to 12.0]
μm] 2. The toner according to claim 1, wherein the sulfur-containing compound is a polymer or copolymer having a sulfonic acid group. 3. The toner according to claim 1, wherein the sulfur-containing compound is a copolymer of an acrylamide sulfonic acid type monomer. 4. The toner according to claim 1, wherein the sulfur-containing compound is a copolymer of 2-acrylamido-2-methylpropanesulfonic acid. 5. The toner according to claim 1, wherein the sulfur-containing compound is a copolymer of a styrene/acrylic monomer and a sulfonic acid-containing acrylamide monomer. 6. The toner according to claim 1, wherein the sulfur-containing compound is a negative charge control agent. 7. A weight average molecular weight of the sulfur-containing compound (M
The toner according to claim 1, wherein w) is 2,000 to 200,000. 8. A weight average molecular weight of the sulfur-containing compound (M
7. The toner according to claim 1, wherein w) is 17,000 to 100,000. 9. The weight average molecular weight (M
7. The toner according to claim 1, wherein w) is 27,000 to 50,000. 10. The toner according to claim 1, wherein the sulfur-containing compound has a glass transition temperature (Tg) of 30° C. to 120° C. 11. The toner according to claim 1, wherein the sulfur-containing compound has a glass transition temperature (Tg) of 50° C. to 100° C. 12. The toner according to claim 1, wherein the sulfur-containing compound has a glass transition temperature (Tg) of 70° C. to 95° C. 13. The sulfur-containing compound is a copolymer of a styrene/acrylic monomer and 2-acrylamido-2-methylpropanesulfonic acid, according to any one of claims 1 to 12. Toner. 14. The sulfur-containing compound has an average particle size of 30.
2. The powder is pulverized to a size of 0 μm or less.
14. The toner according to any one of 1 to 13. 15. The sulfur-containing compound has an average particle size of 15.
2. The powder is pulverized to a size of 0 μm or less.
14. The toner according to any one of 1 to 13. 16. Toner particles are obtained by melt-kneading a mixture containing at least a binder resin, a colorant and a sulfur-containing compound, cooling the kneaded product, coarsely pulverizing the cooled product, and subjecting the resulting coarsely-pulverized product to a machine. The toner according to any one of claims 1 to 15, which is obtained by finely pulverizing with a type pulverizer. 17. The toner particles are obtained by finely pulverizing the coarsely pulverized product by a mechanical pulverizer and classifying the obtained finely pulverized product by an air classifier. 16. The toner according to 16. 18. The toner particles are produced through a melt-kneading step, a fine pulverizing step and a classifying step,
A mixture containing at least a binder resin, a colorant, and a sulfur-containing compound is melt-kneaded, the obtained kneaded product is cooled, and then the cooled product is roughly pulverized by a pulverizing means. A raw material is introduced into a first constant quantity feeder, and a rotor is formed of a rotary body attached to at least a central rotary shaft, and a stator arranged around the rotor with a constant distance from the rotor surface. And a predetermined amount of powder raw material from the first fixed amount feeder in a mechanical crusher configured so that an annular space formed by maintaining a space is in an airtight state. The powder raw material was introduced through a powder introduction port of a mechanical pulverizer and the rotor of the mechanical pulverizer was rotated at high speed to finely pulverize the powder raw material, and the weight average diameter was 5 to 12 μm. 70% by number or less of particles having a size of 4.0 μm or less and 25% by volume or less of particles having a particle size of 10.1 μm or more are produced, and the finely pulverized product is pulverized by a mechanical crusher. A multi-split airflow system that discharges from a powder discharge port and introduces it into a second fixed quantity feeder, and a predetermined amount of finely pulverized material from the second fixed quantity feeder is classified by airflow using the cross flow and Coanda effect. Introduced into the classifier,
The finely pulverized material is classified into at least fine powder, medium powder and coarse powder in the multi-divided airflow classifier, and the classified coarse powder is mixed with the powder raw material and introduced into the mechanical pulverizer. The toner according to claim 17, which is produced from a pulverized and classified medium powder. 19. The toner according to claim 1, wherein 40% by number or less of particles having a particle size of 4.0 μm or less and 25% by volume or less of particles having a particle size of 10.1 μm or more. The toner according to any one. 20. The toner according to claim 1, wherein a standard deviation SD of circularity of the toner is 0.030 to 0.050. 21. The toner according to claim 1, wherein a standard deviation SD of circularity of the toner is 0.030 to 0.045. 22. The sulfur-containing compound has an acid value of 3 to 80.
It is mgKOH/g, The claim 1 or 2 characterized by the above-mentioned.
1. The toner according to any one of 1. 23. The sulfur-containing compound has an acid value of 5 to 40.
It is mgKOH/g, The claim 1 or 2 characterized by the above-mentioned.
1. The toner according to any one of 1. 24. The sulfur-containing compound has an acid value of 10 to 3.
The toner according to any one of claims 1 to 21, wherein the toner is 0 mgKOH/g. 25. The sulfur-containing compound has a volatile content of 0.01.
25 to 2.0% by mass, the toner according to claim 1. 26. The sulfur-containing compound has a volatile content of 0.01.
The toner according to any one of claims 1 to 24, characterized in that 27. The toner according to claim 1, wherein the sulfur-containing compound is contained in an amount of 0.01 to 15 parts by mass based on 100 parts by mass of the binder resin. 28. The toner according to claim 1, wherein the sulfur-containing compound is contained in an amount of 0.10 to 10 parts by mass based on 100 parts by mass of the binder resin. 29. An electrostatic charge image is formed on an electrostatic charge image carrier,
The electrostatic image is developed with the toner held in the developing means to form a toner image, and the formed toner image is transferred onto a transfer material with or without an intermediate transfer member, and the toner image on the transfer material is transferred. An image forming method in which a toner image is fixed on a transfer material by a heating and pressing fixing means, the toner is a toner having at least a binder resin and a colorant, and the toner is a sulfur-containing polymer and a sulfur-containing copolymer. The toner contains a sulfur-containing compound selected from the group consisting of coalesced particles, the toner has a weight average particle diameter of 5 to 12 μm, and in the toner particles of 3 μm or more, the circularity a calculated from the following formula (1) is The number of particles of 0.900 or more is 90% by number or more in terms of cumulative value, and the circularity is a=L ₀ /L (1) [wherein L ₀ is the perimeter of a circle having the same projected area as the particle image] And L represents the perimeter of the particle image. And a) the relationship between the cut ratio Z and the toner weight average diameter X satisfies the following formula (2), and the cut ratio Z≦5.3×X (2) [where the cut ratio Z is manufactured by Toa Medical Electronics Co., Ltd. When the particle concentration A (number/μl) of all the measured particles measured by the flow type particle image analyzer FPIA-1000 and the measured particle concentration B (number/μl) with an equivalent circle diameter of 3 μm or more are given by the following formula (3): Indicated by. Z=(1−B/A)×100 (3)], and in particles of 3 μm or more of the toner, the circularity (a) of 0.950 or more in the number-based circularity distribution of the circularity (a). The relationship between the number-based cumulative value Y of the particles having the average particle size X and the toner weight average diameter X satisfies the following formula (4): The number-based cumulative value Y of the particles having a circularity of 0.950 or more Y≧exp5.51×X ^−0.645 ( 4) [However, the weight average particle diameter X of the toner is X: 5.0 to 12.0.
μm] or b) The relationship between the cut rate Z and the toner weight average diameter X satisfies the following formula (5), and the cut rate Z>5.3×X (5) and the toner particles having a diameter of 3 μm or more are circular. In the number-based circularity distribution of the degree (a), the relationship between the number-based cumulative value Y of the particles having the circularity (a) of 0.950 or more and the toner weight average diameter X satisfies the following expression (6). And an image forming method. Number-based cumulative value of particles having a circularity of 0.950 or more Y≧exp 5.37×X ^−0.545 (6) [However, weight average particle diameter X of toner: 5.0 to 12.0]
μm] 30. The electrostatic charge image carrier is charged by a contact charging means to which a bias is applied, and the charged electrostatic charge image carrier is exposed to form a digital latent image, and the digital latent image is developed. To develop a toner image with the toner held in the
31. Alternatively, the transfer is performed by a contact transfer means in which a bias is applied to the transfer material without intervention.
The image forming method described in 1. 31. The toner is a magnetic toner having magnetic toner particles containing a magnetic material, and the developing means has a developing sleeve containing a magnetic field generating means, and a magnetic toner layer is formed on the developing sleeve. 3. An elastic blade for effecting
31. The image forming method described in 9 or 30. 32. An image forming method, wherein the toner is the toner according to any one of claims 2 to 28. 33. An electrostatic charge image carrier, at least a developing unit for developing an electrostatic charge image formed on the electrostatic image carrier with toner, and a container for holding a dry toner, A process cartridge having a structure in which the electrostatic image carrier, the developing means, and the container are integrally supported, the process cartridge is attachable to and detachable from the main body of the image forming apparatus, and the toner is a binder resin. A toner having at least a colorant, the toner containing a sulfur-containing compound selected from the group consisting of a sulfur-containing polymer and a sulfur-containing copolymer, and the toner has a weight average particle diameter of 5 to 12 μm. In the particles of 3 μm or more of the toner, particles having a circularity a calculated by the following formula (1) of 0.900 or more have a number-based cumulative value of 90% by number or more, and the circularity a=L ₀ / L (1) wherein, L ₀ represents the circumferential length of a circle having the same projected area as a particle image, L is indicative of the ambient length of the particle image. And a) the relationship between the cut ratio Z and the toner weight average diameter X satisfies the following formula (2), and the cut ratio Z≦5.3×X (2) [where the cut ratio Z is manufactured by Toa Medical Electronics Co., Ltd. When the particle concentration A (number/μl) of all the measured particles measured by the flow type particle image analyzer FPIA-1000 and the measured particle concentration B (number/μl) with an equivalent circle diameter of 3 μm or more are given by the following formula (3): Indicated by. Z=(1−B/A)×100 (3)], and in particles of 3 μm or more of the toner, the circularity (a) of 0.950 or more in the number-based circularity distribution of the circularity (a). The relationship between the number-based cumulative value Y of the particles having the average particle size X and the toner weight average diameter X satisfies the following formula (4): The number-based cumulative value Y of the particles having a circularity of 0.950 or more Y≧exp5.51×X ^−0.645 ( 4) [However, the weight average particle diameter X of the toner is X: 5.0 to 12.0.
μm] or b) The relationship between the cut ratio Z and the toner weight average diameter X satisfies the following formula (5), and the cut ratio Z>5.3×X (5) and the toner particles having a diameter of 3 μm or more are circular. In the number-based circularity distribution of the degree (a), the relationship between the number-based cumulative value Y of the particles having the circularity (a) of 0.950 or more and the toner weight average diameter X satisfies the following expression (6). Process cartridge characterized by. Number-based cumulative value of particles having a circularity of 0.950 or more Y≧exp 5.37×X ^−0.545 (6) [However, weight average particle diameter X of toner: 5.0 to 12.0]
μm] 34. The process cartridge according to claim 33, wherein the electrostatic charge image carrier is a photosensitive drum. 35. The process cartridge according to claim 33 or 34, further comprising a contact charging means. 36. The process cartridge according to claim 33, wherein the toner is the toner according to any one of claims 2 to 28.