JP2002040702A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which is excellent in low temperature fixation and has high efficiency of transfer. SOLUTION: In this toner comprising at least binding resin, colorant and wax, the wax is included in the amount of 0.2-20 pts.mass per the binding resin content of 100 pts.mass, the maximum endothermic peak temperature in the DSC curve of the toner which is measured by a differential scanning calorimeter is 60-100 deg.C and the weight average particle size X of the toner is 5-12 μm. Further, in the particles of which the diameter corresponding to circle of the toner is >=3 μm, the particles of which the roundness (a) calculated by the following relation (1) is >=0.900 is included in the amount of >=90% in the cumulative value of number basis and the cumulative value Y of number basis of the particles having the roundness of >=0.950 is satisfied by he specified relation with the weight average particle size X of the toner: the roundness (a)=L0/L (1), where L0 denotes the peripheral length of the circle having a projection area equivalent to that of particle image and L denotes the peripheral length of the particle image.

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.

[0002]

2. Description of the Related Art As an electrophotographic method, US Pat.
Many methods are known as described in JP-B-7691, JP-B-42-23910 and JP-B-43-24748. Generally, a photoconductive substance is used to form an electrostatic latent image on a photoreceptor by various means,
Next, the latent image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure, heating pressure, or solvent vapor to obtain a toner image.

[0003] In recent years, devices using such an electrophotographic method include, besides a copying machine for copying an original manuscript,
It has begun to be used in computer output printers and facsimile machines. So smaller, lighter,
Faster and more reliable are being sought after, and machines are becoming simpler in various respects. As a result, the performance required of the toner becomes higher, and if the performance of the toner cannot be improved, a better machine cannot be realized.

When a toner image is transferred onto a transfer material from a photoreceptor, there is toner remaining on the photoreceptor without being transferred. In order to quickly perform continuous copying, it is necessary to clean the residual toner on the photoconductor. The collected residual toner is disposed in a container or a collection box installed in the main body and then discarded, or is recycled through an appropriate process.

In order to address environmental issues, it is necessary to design a main unit having a recycling system inside the main unit as a waste tonerless system.

However, in order to achieve the multifunctional, high-speed, and high-quality copy images required for the copying machines, printers, and facsimile machines required in the market, a fairly large-scale recycling system is required in the main body. The size itself becomes large, which goes against the miniaturization required in the market. The same applies to a system in which waste toner is stored in a container or a collection box installed in the main body, or a system in which a photosensitive member and a portion for collecting the waste toner are integrated.

In order to cope with these problems, it is necessary to improve the transfer rate when a toner image is transferred from a photoreceptor to a transfer material.

Japanese Patent Application Laid-Open No. 9-26672 discloses that a toner containing 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 is used. There is disclosed a method of reducing the resistance and improving the transfer efficiency by forming a thin film layer with a transfer efficiency enhancer on a photoreceptor. However, since the toner produced by the pulverization method has a particle size distribution, it is difficult to exert an effect uniformly on all the particles, and further improvement is required.

As a method for improving the transfer efficiency, toners obtained by manufacturing methods such as spray granulation, solution dissolution, and polymerization have been disclosed in Japanese Patent Application Laid-Open Nos. No. 229268, JP-A-4-1766, JP-A-4-102862, and the like. However, the production of these toners requires not only large-scale equipment, but also problems related to cleaning because the toner approaches a true sphere. Not a way.

Generally, a toner is produced by using, as raw materials, a binder resin for fixing to a material to be transferred, various colorants for giving a color as a toner, and a charge control agent for giving a charge to particles. Alternatively, in a so-called one-component developing method as disclosed in JP-A-54-42141 and JP-A-55-18656, in addition to these, various magnetic materials for imparting transportability or the like to the toner itself are used. Used, and further, if necessary, for example, dry-mixing by adding other additives such as a release agent and a fluidity-imparting agent, and thereafter, a roll mill,
After melt-kneading with a general-purpose kneading device such as an extruder and cooling and solidifying, the kneaded material is refined with various types of pulverizing devices such as a jet stream type pulverizer and a mechanical collision type pulverizer, and the obtained finely pulverized product is subjected to various types of wind power. By introducing the toner into a classifier and performing classification, a classified product having a particle size required for the toner is obtained. Further, if necessary, a fluidizing agent, a lubricant, etc. are externally added and dry-mixed to form an image. And the toner to be used for Also,
In the case of the toner used in the two-component developing method, various magnetic carriers are mixed with the above toner, and then used for image formation.

As described above, in order to obtain toner particles which are fine particles, the method shown in the flowchart of FIG. 7 has conventionally been generally employed.

The coarsely crushed toner is continuously or sequentially supplied to the first classifying means, and the classified coarse powder having a coarse particle group having a specified particle size or more as a main component is sent to the crushing means and crushed. It is circulated to the classifier.

The finely pulverized toner mainly composed of particles within the specified particle size range and particles smaller than the specified particle size is sent to the second classifying means, and the medium powder mainly composed of particles having the specified particle size is sent to the second classifying means. Body, a fine powder mainly composed of a group of particles having a specified particle size or less,
It is classified into a coarse powder mainly composed of particles exceeding a specified particle size.

Various pulverizing devices are used as a pulverizing means. For pulverizing a coarsely crushed toner mainly composed of a binder resin,
A jet air flow type pulverizer using a jet air flow as shown in FIG. 8, particularly a collision type air flow pulverizer is used.

A collision type air flow pulverizer using a high-pressure gas such as a jet gas stream conveys a powder material by a jet gas stream, injects the powder material from an outlet of an accelerating tube, and opposes an opening surface of an outlet of the accelerating tube. Then, the powder material is crushed by the impact force of the collision member.

For example, in the collision type air flow pulverizer shown in FIG. 10, an acceleration pipe 162 connected to a high pressure gas supply nozzle 161 is used.
A collision member 164 is provided opposite to the outlet 163 of the, 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 communicated in the middle of the acceleration pipe 162. The powder raw material is ejected together with the high-pressure gas to collide with the collision surface 166 of the collision member 164, and is pulverized by the impact, and the pulverized material is discharged from the pulverized material discharge port 167 from the pulverization chamber 168.

However, the above-mentioned crushing airflow pulverizer has a structure in which the powdery 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, so that the pulverized toner cannot be used. It is a regular and square shape.

Japanese Patent Application Laid-Open No. 2-87157 discloses that a toner produced by a pulverization method is subjected to mechanical shock (hybridizer).
Discloses a method for improving the transfer efficiency by modifying the shape and surface properties of particles. However, in this method, a further processing step is performed after the pulverization, so that the toner surface approaches a state having no unevenness due to toner productivity and processing, and improvement in the development surface is required, which is not a preferable method.

In addition, a large amount of air is required to produce a toner having a small particle diameter by the above-mentioned impingement airflow pulverization. Therefore, power consumption is extremely large, and there is a problem in terms of energy cost. In particular, in recent years, energy saving of devices has been demanded in response to environmental problems.

Regarding the classification means, various airflow classifiers and methods have been proposed. Among these, there are a classifier using a rotary wing and a classifier without a movable part. Among them, a classifier without a movable part includes a fixed wall centrifugal classifier and an inertial force classifier. Classifiers utilizing such inertia are disclosed in JP-B-54-24745 and JP-B-55-64.
No. 33, and JP-A-63-101858.

As shown in FIG. 11, these air-flow classifiers discharge powder at high speed from a supply nozzle having an opening in a classification area of a classifier chamber into a classification area with a gas stream. 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 is separated by the narrowed edges 146 and 147.
Classifying medium powder and fine powder.

In the conventional classifier 57, the finely pulverized raw material is introduced from the raw material supply nozzle, and the granular material flowing inside the pyramids 148, 149 has a tendency to flow with propulsion straight and parallel to the tube wall. 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 lot of light fine powder, and the lower flow contains a lot of heavy coarse powder. Easy, because each particle flows independently, draw different trajectories depending on the introduction site into the classifier, or coarse powder disturbs the trajectory of fine powder, there is a limit to improve the classification accuracy, In addition, in the case of classifying a powder having a large amount of coarse particles of 20 μm or more, accuracy tends to decrease.

In general, a toner requires many different properties, and in order to obtain such required properties, the raw materials to be used as well as the production method are often determined. In the toner classification process, the classified particles are required to have a sharp particle size distribution. It is also desired to efficiently and stably produce high quality toner at low cost.

Further, in order to improve the image quality in copying machines and printers, it is required that the toner has a fine particle size and a particle size distribution that does not contain coarse particles and has a small amount of ultrafine powder. Is done. Generally, as the material becomes finer, the action of the interparticle force increases,
The same applies to resin and toner. When the size of the fine powder is reduced, the cohesiveness of the particles increases.

In particular, when trying to obtain a toner having a sharp particle size distribution with a weight average diameter of 12 μm or less, the conventional apparatus and method cause a reduction in classification yield. Furthermore, when trying to obtain a toner having a sharp particle size distribution with a weight average diameter of 10 μm or less, not only the conventional apparatus and method not only cause a decrease in the classification yield, but also
It tends to contain a large amount of ultrafine powder.

Even if a desired product having a fine particle size distribution can be obtained under the conventional method, the steps become complicated, the classification yield is reduced, the production efficiency is poor, and the cost tends to be high. is there. This tendency becomes more pronounced as the predetermined particle size becomes smaller.

Further, in the case of finely divided toner, the colorant (magnetic substance) contained in the toner is relatively large, and it is difficult to maintain the low-temperature fixing property of the toner, and the developing property is more severe than before. You will be restricted.

That is, in such an electrophotographic apparatus, there is a need for a highly developable toner having good fixability and improved transfer efficiency.

[0029]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner having excellent low-temperature fixability and high transfer efficiency.

An object of the present invention is to provide a toner which can maintain good developability even with fine particles.

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

[0032]

The present invention relates to a toner having at least a binder resin, a colorant and a wax.
The wax was added in an amount of 0.2 to 100 parts by mass of the binder resin component.
-20 parts by mass, and the maximum endothermic peak temperature of the DSC curve of the toner measured by a differential scanning calorimeter is 60 to 1
00 ° C., and the weight average particle diameter X of the toner is 5 to 12
of particles having a circularity a of 0.900 or more calculated from the following formula (1) in terms of the number-based cumulative value of particles having a particle diameter of 3 μm or more and a particle size of 3 μm or more. Degree a = L ₀ / L (1) [where L ₀ represents the circumference of a circle having the same projected area as the particle image, and L represents the circumference of the particle image. And a toner satisfying the following a) or b). a) The relationship between the cut rate Z and the toner weight average particle diameter X satisfies the following expression (2), and the cut rate Z ≦ 5.3 × X (2) [where the cut rate Z is the particle concentration of all the measured particles. Is A (number / μl), and the concentration of measured particles having a circle equivalent diameter of 3 μm or more is B
(Number / μl), it is expressed by the following equation (3). Z = (1−B / A) × 100 (3)
And the number-based cumulative value Y of the particles having a circularity of 0.950 or more.
The toner weight-average or relationships particle diameter X satisfies the following expression (4), a number basis cumulative value Y ≧ circularity 0.950 or more particles exp5.51 × X ^{-0.6 45} (4), or, b) The relationship between the cut rate Z and the toner weight average diameter X satisfies the following expression (5), and the cut rate Z> 5.3 × X (5) and the number-based cumulative value Y of the particles having a circularity of 0.950 or more.
The toner weight-average relationship particle diameter X satisfies the following formula (6), a number basis cumulative value Y ≧ circularity 0.950 or more particles exp5.37 × X ^{-0.5 45} (6)

Preferably, the present invention has at least one peak in a molecular weight range of 3,000 to 50,000 in a molecular weight distribution measured by GPC of a THF-soluble component of the toner, and has a molecular weight of 50,000. 000-10,0
A toner having at least one peak or shoulder in the region of 00000.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have studied the shape of toner produced by the pulverization method and the raw materials constituting the toner, and have found that these have a close relationship with transferability and developability (image quality). I found it. Further, by using a pulverizing / classifying system for optimally producing the toner, this was achieved in a simple and unconventional method.

Here, the pulverizing / classifying system capable of optimally producing the toner of the present invention melts and kneads a mixture containing at least a binder resin, a colorant and a wax, cools the obtained kneaded material, and then cools the mixture. The material is coarsely pulverized by a pulverizing means, and the obtained powdery raw material composed of the coarsely pulverized material is introduced into a first quantitative feeder, and at least a rotor composed of a rotating body attached to a central rotating shaft; Mechanical grinding, comprising a surface and a stator arranged around the rotor at a constant distance, and configured so that an annular space formed by maintaining the distance is airtight. Into the machine, a predetermined amount of powder raw material is introduced from the first metering device through a powder inlet of the mechanical crusher, and the rotor of the mechanical crusher is rotated at a high speed to obtain powder. Raw material is finely pulverized and the fine powder The finely pulverized product is introduced into the second metering feeder and discharged from the powder discharge port of the mechanical pulverizer, the second
A predetermined amount of the finely pulverized material from the metering feeder is introduced into a multi-divided air flow type classifier that classifies the powder by utilizing the crossed airflow and the Coanda effect, and at least the finely pulverized material is divided in the multi-divided air flow type classifier. Classify into fine powder, medium powder and coarse powder, mix the classified coarse powder with the powder raw material, introduce it into the above mechanical pulverizer, pulverize it, and generate toner from the classified medium powder System. Details will be described later.

As the particle size of the toner is reduced, the specific surface area of the toner particles increases. This increases the cohesiveness and adhesion of the toner. For this reason, when the toner image is transferred from the photoreceptor to the transfer material, the adhesive force acting between the photoreceptor and the toner is increased, and the transfer efficiency is reduced. In particular, the toner produced by the conventional pulverization method is irregular and angular, and this tendency is remarkable.

In other words, even if the toner has a small particle size, it is possible to improve the transfer efficiency by giving a low or equal adhesion to the conventional toner having a particle size.

By making the toner spherical, the contact area between the toner and the photoreceptor can be reduced, and the transfer efficiency can be improved. However, it is very difficult to produce a true spherical toner using a pulverized toner. Therefore, a method has been considered in which corners of the pulverized toner are removed and the surface is made smoother by smoothing the surface. As a result, the transfer efficiency of the toner can be improved, but there are various problems due to the pulverization method, and further investigation is required.

When a toner having a small particle diameter is used, dot reproducibility is improved, but fog and scattering tend to be deteriorated. This is considered to be due to the fact that toner such as fine powder and ultrafine powder and a large number of particles having a desired particle diameter are mixed in order to produce a fine particle toner from a coarsely pulverized toner having a large particle size. In other words, toners having different particle diameters have different charging characteristics and different adhesions to individual particles. For this reason, by reducing the particle size, the distribution of the charge amount of the toner becomes wider on the contrary.

By repeatedly classifying the pulverized toner, a sharp particle size distribution can be obtained, but it is difficult to adapt it to actual toner production.

That is, according to the study of the present inventor, in the toner manufactured by the pulverization method, the generation of waste toner is improved by improving the transfer rate when the toner image is transferred from the photosensitive member to the transfer material. To suppress, and, in order to achieve good low-temperature fixability and high developability, the toner pulverized by a manufacturing apparatus that combines a specific pulverizer and a specific classifier has a specific circularity, Further, it is important to contain a toner constituent material described later.

The circularity in the present invention is used as a simple method for quantitatively expressing the shape of a particle. In the present invention, the flow particle image analyzer “FPA” manufactured by Toa Medical Electronics Co., Ltd.
IA-1000 ”, the circularity of the measured particles is determined by the following equation (1), and as shown by the following equation (7), the sum of the measured circularities of all the particles is calculated as The value divided by the number m of particles is defined as the average circularity.

Circularity a = L ₀ / L (1) [where L ₀ indicates the circumference of a circle having the same projected area as the particle image, and L indicates the circumference of the particle image. ]

[0044]

(Equation 1)

The circularity standard deviation SD is given by the following equation (8).
Is calculated from

[0046]

(Equation 2)

The circularity a used in the present invention is an index of the degree of unevenness of the toner particles, and is 1.00 when the toner is perfectly spherical. Become. Further, the standard deviation SD of the circularity distribution in the present invention is an index of the variation, and the smaller the numerical value, the smaller the variation of the toner shape and the sharper the distribution. In the present invention, the circularity standard deviation SD
Is 0.034 to 0.043, there is no problem.

The measuring device "FPIA-1000" used in the present invention calculates the circularity of each particle,
In calculating the average circularity and the circularity standard deviation, the particles were converted to a circularity of 0.4 to 1.0 by 6 according to the obtained circularity.
Each value of the average circularity and circularity standard deviation using the center value and frequency of the dividing point, and the average circularity and the circularity calculated by the above-described calculation formula that directly uses the circularity of each particle. The error of the circularity standard deviation is very small,
It is practically negligible, and in the present invention,
For the reason of data handling such as shortening of calculation time and simplification of calculation operation formula, the above-mentioned calculation method partially modified using the concept of calculation formula directly using the circularity of each particle described above was used. May be used.

As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersing agent to 100 to 150 ml of water from which impurities have been removed in a container in advance, and the measurement is further performed. 0.1
Add about 0.5 g. The suspension in which the sample was dispersed was irradiated with ultrasonic waves (50 kHz, 120 W) for 1 to 3 minutes, the concentration of the dispersion was adjusted to 1.2 to 20 thousand / μl, and the above-mentioned flow type particle image measuring apparatus was used. 0.60 μm or more and 159.21
The circularity distribution of particles having a circle equivalent diameter of less than μm is measured. In addition, by setting the concentration of the dispersion liquid to 12 to 20 thousand particles / μl, it is possible to maintain the particle concentration enough to maintain the accuracy of the apparatus even when the cut rate becomes large.

The outline of the measurement is described in the catalog of FPIA-1000 (June 1995 edition) issued by Toa Medical Electronics Co., Ltd., the operation manual of the measuring apparatus and Japanese Patent Application Laid-Open No. 8-136.
No. 439, which is as follows.

The sample dispersion is passed through a flow path (spread along the flow direction) of a flat and flat flow cell (about 200 μm thick). The strobe and the CC are connected so as to form an optical path that intersects with the thickness of the flow cell.
The D cameras are mounted so as to be located on opposite sides of the flow cell. While the sample dispersion is flowing,
Strobe light is applied at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle is captured as a two-dimensional image having a range parallel to the flow cell. The diameter of a circle having the same area is calculated as the equivalent circle diameter from the area of the two-dimensional image of each particle. 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-described circularity calculation formula.

Conventionally, it has been known that the shape of the toner affects various properties of the toner. However, the present inventors have made various studies to exceed a certain amount of particles having a circle equivalent diameter of less than 3 μm. It has also been found that this causes a deterioration in performance such as transferability and developability. That is, when particles having a particle size of less than 3 μm, such as fine powder of toner and external additives, have a certain amount or more, it is apparent that it is difficult to obtain desired performance unless the circularity of the toner having a particle size of 3 μm or more is further increased.

Therefore, in the present invention, the degree of circularity of a group of particles having a circle equivalent diameter of 3 μm or more is important for exhibiting the effects of the present invention. In order to more effectively exert the above-described effect of the circularity of the toner particles, the following 3 μm is required.
It is necessary to control the circularity of toner particles having a particle size of 3 μm or more based on the amount of particles having a particle size of less than m.

That is, depending on the amount of particles less than 3 μm, 3
By controlling the circularity of the toner particles having a size of μm or more, a toner having excellent transferability and developability can be obtained.

In the present invention, the abundance of particles smaller than 3 μm is
As shown in the following formula (3), the ratio of the particle concentration of the particle group having a circle equivalent diameter of 3 μm or more to the particle concentration of all the measured particles is obtained by subtracting from 100%, and this is defined as the cut ratio. Cut ratio Z = (1−B / A) × 100 (3) [where A represents the particle concentration (number / μl) of all the measured particles, and B represents the particle concentration of a particle group having a circle equivalent diameter of 3 μm or more. (Number / μl). ]

That is, the toner of the present invention contains 90% or more of particles having a circularity a of 0.900 or more in particles having a circle equivalent diameter of 3 μm or more in a number-based cumulative value of 90% or more. When the relationship between the ratio Z and the toner weight average particle diameter X satisfies the formula of cut rate Z ≦ 5.3 × X (2) (however, the toner weight average particle diameter X is 5.
0～12.0Myuemu), circularity a is the number base cumulative value Y of 0.950 or more particles, the number reference accumulated value of circularity of 0.950 or more particles Y ≧ exp5.51 × X ^{-0 .645} It is important to satisfy (4). Or b) when the relationship between the cut rate Z and the toner weight average diameter X satisfies the following equation: Cut rate Z> 5.3 × X (5) (where the toner weight average particle diameter X is 5.
0～12.0Myuemu), circularity a is the number base cumulative value Y of 0.950 or more particles, the number reference accumulated value of circularity of 0.950 or more particles Y ≧ exp5.37 × X ^{-0 .545} It is important to satisfy (6).

In the measurement of circularity in "FPIA-1000", the smaller the particle diameter, the closer the particle image is to a point, and thus the greater the circularity tends to be. Therefore, when a large amount of particles having a small particle diameter are present in the toner, the circularity of the toner is increased. Conversely, when only a small amount of particles having a small particle diameter are present in the toner, the circularity of the toner is reduced. Therefore, the content of particles having a particle size of less than 3 μm, that is, the cut rate Z represented by the formula (3)
And the relationship between the weight average particle size X and the weight average particle diameter X are divided into two cases of Expression (2) or Expression (5).
The relationship between the toner shape necessary for satisfying the desired performance, that is, the circularity and the weight average particle diameter, was derived as in the equation (4) or (6).

In a toner containing a small amount of particles having a particle size of less than 3 μm, the circularity of the particles having a particle size of 3 μm or more is 0.9.
The cumulative value Y based on the number of particles of 50 or more is a weight average diameter X
Exp5.51 may if × X ^-0.645 above, in the toner containing a large amount of 3μm particles smaller than in the 3μm or more particles, circularity accumulated based on the number of 0.950 or more particles against The value Y needs to be larger than exp5.37 × X ^{−0.545 which} is larger than the weight average diameter X.

Since the toner of the present invention has the above-mentioned circularity, the specific surface area of the toner particles is reduced as compared with the toner pulverized by the conventional collision type air pulverizer. For this reason, the contact area between the toner particles is reduced, the bulk density of the toner powder is increased, and the heat conduction during fixing can be improved. That is, the fixing property is improved. Further, the contact area between the toner particles and the photoconductor is reduced, and the adhesion of the toner particles to the photoconductor due to van der Waals force or the like is reduced, so that the transfer efficiency is increased.

In the case where the number of particles having a circularity a of 0.900 or more in a particle having a circle equivalent diameter of 3 μm or more is less than 90% in terms of the number-based cumulative value, the toner particles and the photosensitive member are Since the contact area increases and the adhesive force of the toner particles to the photoconductor increases, sufficient transfer efficiency cannot be obtained.

Further, regarding the number-based cumulative value Y of the particles having a circularity a of 0.950 or more in the particles having a circle equivalent diameter of 3 μm or more in the toner, a) Relationship between cut rate Z and toner weight average particle diameter X When the following expression (4) is not satisfied while satisfying the expression (2), that is, the expression of the cut ratio Z ≦ 5.3 × X, the number-based cumulative value Y ≧ exp5 of the particles having a circularity of 0.950 or more is satisfied. .51 × X ^{-0 .645} (4) that is, the number reduced cumulative value Y of circularity 0.950 or more particles <e
If xp5.51 × X ^{-0 .645} to become such, or, b) cut rate Z and the toner weight relationship average diameter X has the formula (5), i.e., cut rate Z> 5.3 × X (preferably 9
When the following expression (6) is not satisfied while satisfying the expression of 5 ≧ cut ratio Z> 5.3 × X), the number-based cumulative value of particles having a circularity of 0.950 or more Y ≧ exp 5.37 × X ^{− 0.545} (6) that is, the number reduced cumulative value Y of circularity 0.950 or more particles <e
If xp5.37 × X ^{-0 .545} become such also decreases the flowability of the toner not only sufficient transfer efficiency can be obtained and the desired fixing performance can not be obtained.

When the toner of the present invention is manufactured, the weight average particle diameter of the toner is preferably 5 to 12 μm. More preferably, the toner has a weight average particle size of 5 to 10 μm, particles having a particle size of 4.0 μm or less are 40% by number or less, and particles having a particle size of 10.1 μm or more are 35% by volume or less. .

In order to obtain a toner having a weight average diameter of more than 12 μm, it is possible to cope with the particle size by reducing the load in the pulverizer as much as possible or by increasing the amount of processing, but the shape is square. It becomes difficult to obtain a desired circularity, and as a result, a high transfer rate and good fixability cannot be obtained.

To obtain a toner having a weight average diameter of less than 5 μm, it is possible to cope with the problem by increasing the load in the pulverizer or by extremely reducing the processing amount. It becomes difficult to hold down, resulting in adverse effects such as deterioration of fog and scattering.

In the case where a toner having a particle size of 4.0 μm or less and more than 40% by number is obtained, it is possible to cope by increasing the load in the pulverizer or by extremely reducing the processing amount. In addition, it becomes impossible to avoid the deterioration of the fogging and scattering phenomenon caused by the generation of the ultrafine powder.

Furthermore, 35 particles having a particle diameter of 10.1 μm or more
To obtain a toner exceeding volume%, the particle size can be dealt with by minimizing the load in the pulverizer or increasing the processing amount, but the shape becomes angular and the desired circularity is obtained. This makes it difficult to obtain a high transfer rate and good fixability.

The particle size distribution was measured by the following method.

The particle size distribution can be measured by various methods. In the present invention, the particle size distribution was measured using a Coulter counter multisizer.

As a measuring apparatus, a Coulter counter Multisizer II or IIE (manufactured by Coulter) was used, and an interface (manufactured by Nikkaki) for outputting the number distribution and volume distribution and a general personal computer were connected. As the electrolyte, a 1% NaCl aqueous solution is prepared using a special grade or primary grade sodium chloride. As a measurement method, 0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is further added to 2 to 20 m.
Add g. The electrolyte in which the sample is suspended is approximately 1
Dispersion treatment is carried out for up to 3 minutes, and the measurement is carried out using a Coulter Counter Multisizer II with a 100 μm aperture. The volume and number of the toner are measured, the volume distribution and the number distribution are calculated, and the weight-based weight average diameter determined from the volume distribution is determined.

The toner of the present invention has a maximum endothermic peak temperature of 60 to 1 on a DSC curve measured by a differential scanning calorimeter.
00 ° C, preferably 65-95 ° C, more preferably 70 ° C
~ 90 ° C. In order for the toner to have such a DSC endothermic peak, DS measured by a differential scanning calorimeter of a wax component contained in the toner is used.
The maximum endothermic peak temperature of the C curve is preferably from 60 to 100 ° C. The presence of the wax having a relatively low maximum endothermic peak temperature in the toner makes it possible to quickly melt the toner at the time of fixing the toner, thereby improving the fixing performance. Further, the pulverizability in the fine pulverization step in the production of toner is also improved, which is preferable from the viewpoint of toner production efficiency. In addition, since the pulverized toner has the above-described specific circularity, a uniform charge distribution is obtained, and high developability is obtained.

As described above, the toner or the wax contained in the toner has the effect of improving the fixing property due to the relatively low maximum endothermic peak temperature, and the fact that the toner has a specific circularity, thereby synergistically improving the fixing property. The effect of further improving the developability appears. That is, since the heat conduction is improved by increasing the circularity, the melting of the wax is promoted, the plastic effect is easily exerted, and the fixing property is improved. Also, the addition of wax increases the cohesiveness of the toner, but the increase in circularity improves the releasability of the toner particles, reduces the cohesiveness,
Developability is improved. Further, the releasing effect is exhibited by the wax on the surface of the toner particles due to the increase in the circularity, and the transferability can be further improved.

When the maximum endothermic peak temperature in the DSC curve of the toner is less than 60 ° C., there is no problem in the fixing performance, but the anti-offset performance and anti-blocking performance deteriorate.

On the other hand, when the maximum endothermic peak temperature of the DSC curve of the toner exceeds 100 ° C., the effect of improving the fixing property is reduced.

The content of the wax component used in the present invention in the toner must be 0.2 to 20 parts by mass with respect to 100 parts by mass of the binder resin component.

When the amount is less than 0.2 parts by mass, the releasing effect containing the wax is not exhibited, the offset resistance at a high temperature cannot be obtained, and the fixing property is lowered. If the amount exceeds 20 parts by mass, it is difficult to uniformly disperse the wax component in the toner, which affects the chargeability, increases the cohesiveness of the toner, deteriorates the developability, and further deteriorates the toner. Fog due to charging also increases.

The maximum endothermic peak temperature of the DSC curve of the toner and the wax by the differential scanning calorimeter was measured by the following method.

Differential scanning calorimeter (DSC measuring device), DS
ASTM D using C-7 (PerkinElmer)
It is measured according to 3418-82. The measurement sample is precisely weighed in the case of wax, 2 to 5 mg, and in the case of toner, 5 to 10 mg. This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 200 ° C. In this heating process, the maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.

The waxes used in the present invention include the following. For example, oxidation of aliphatic hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; and aliphatic hydrocarbon wax such as polyethylene oxide wax. Object; or
Plant block waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; animal waxes such as beeswax, lanolin, whale wax; mineral waxes such as ozokerite, ceresin, petrolactam; montan Waxes mainly containing fatty acid esters such as acid ester waxes and caster waxes; and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax. Further, unsaturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and barinaric acid; stearyl alcohol; Eicosyl alcohol, behenyl alcohol, carnaubavir alcohol, seryl alcohol, melisyl alcohol,
Or a saturated alcohol such as a long-chain alkyl alcohol having a long-chain alkyl group; a polyhydric alcohol such as sorbitol; linoleamide, oleamide,
Aliphatic amides such as lauric amide; saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric amide, ethylenebislauric amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid Amide, N, N′-dioleyladipamide, N,
Unsaturated fatty acid amides such as N'-dioleyl sebacamide; m-xylene bisstearic acid amide;
Aromatic bisamides such as N'-distearyl isophthalic acid amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metallic soaps); aliphatic hydrocarbon waxes Wax grafted with a vinyl monomer such as styrene or acrylic acid; partially esterified product of a fatty acid such as behenic acid monoglyceride and polyhydric alcohol; methyl having a hydroxyl group obtained by hydrogenating vegetable oil or fat Ester compounds are exemplified.

The wax preferably used is a polyolefin obtained by radical polymerization of an olefin under high pressure;
A polyolefin obtained by purifying a low-molecular-weight by-product obtained during polymerization of a high-molecular-weight polyolefin; a polyolefin polymerized under low pressure using a catalyst such as a Ziegler catalyst or a metallocene catalyst; a polyolefin polymerized by using radiation, electromagnetic waves or light; Low molecular weight polyolefin obtained by pyrolysis of polyolefin; paraffin wax, microcrystalline wax, Fischer-Tropsch wax; synthetic hydrocarbon wax synthesized by the gindol method, hydrocoll method, Aage method, etc .; A synthetic wax, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group;
A mixture of a hydrocarbon wax and a wax having a functional group; a wax obtained by graft-modifying a vinyl monomer such as styrene, maleic ester, acrylate, methacrylate, or maleic anhydride using these waxes as a base.

Particularly preferred are paraffin wax, Fischer-Tropsch wax and polyethylene wax.

Further, these waxes are used in a press sweating method,
Solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method or liquid crystal method using sharpened molecular weight distribution,
Those from which low molecular weight solid fatty acids, low molecular weight solid alcohols, low molecular weight solid compounds, and other impurities have been removed are also preferably used.

The penetration of the wax at 25 ° C. is 10
It is preferably less than mm. More preferably, 8m
m or less. When the penetration is 10 mm or more, the anti-offset performance at high temperatures is deteriorated, and further, the powder fluidity and the cohesion of the toner are adversely affected, and the fading phenomenon, fogging, and the like are easily deteriorated.

The penetration of the wax is determined according to JIS K2207.
It is measured according to. Specifically, the depth when a needle having a conical tip having a diameter of about 9 ° is penetrated with a constant load is set to 0.
It is a numerical value expressed in units of 1 mm. The test conditions were a sample temperature of 25 ° C., a load of 100 g, and a penetration time of 5 seconds.

The wax has a number average molecular weight (Mn) measured by GPC of 100 to 10 in terms of polyethylene.
It is preferably 00, more preferably 200 to 800.

When Mn is less than 100, it is difficult to obtain a sufficient releasing effect, and it is also difficult to disperse the toner in the toner. On the other hand, if Mn exceeds 1000, the fixability is adversely affected, which is not preferable.

The molecular weight of the wax in the present invention was measured by the following method.

<GPC Measurement Conditions for Wax> Apparatus: GPC-150C (manufactured by Waters) Column: GMH-HT (manufactured by Tosoh Corporation) × 2 Temperature: 135 ° C. Solvent: o-dichlorobenzene (addition of 0.1% ionol) Flow rate: 1.0 ml / min Sample: Inject 0.4 ml of a sample having a concentration of 0.15 mass% Under the above conditions, a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for converting the molecular weight of the sample. Furthermore, the molecular weight of the wax is
It is calculated by conversion with a conversion formula derived from the Houwink viscosity formula.

Further, the toner of the present invention has a molecular weight distribution of 3,000 to 50,000, preferably 3,000, in the molecular weight distribution of the THF-soluble component measured by GPC.
It has at least one peak in the range of 0 to 30,000, and has a molecular weight of 50,000 to 10,000,000, preferably a molecular weight of 100,000 to 5,000,000, and more preferably 100,000 to 1,000. It is preferable to have at least one peak or shoulder in the region of 2,000. When the toner has such a peak in the molecular weight distribution, the fixing property, the anti-offset property, and the storability can be maintained in a well-balanced state, and the toner can be provided with durability and charge uniformity.

The peak molecular weight of the high molecular weight component is 50,000
When the value is less than 0, not only the high-temperature offset resistance of the toner is not satisfactory, but also the dispersibility and retention of the wax component according to the present invention are insufficient, and image defects such as a decrease in image density are likely to occur. Become. On the other hand, when the peak molecular weight is 1
If it exceeds 0,000,000, the high-temperature offset resistance is good, but the fixability is deteriorated, and the pulverizability at the time of toner production is reduced, which may cause a decrease in productivity.

The low molecular weight component has a peak molecular weight of 3,
When the molecular weight is less than 000, plasticization by the wax component becomes abrupt, which causes a problem in high-temperature offset resistance and storage stability. Further, since phase separation easily occurs locally, the triboelectric charging of the toner becomes non-uniform, and the developing characteristics may deteriorate. On the other hand, when the peak molecular weight of the low molecular weight component exceeds 50,000, the dispersion state of the wax component is improved to some extent, and although the developing characteristics are improved, the fixability is not sufficient. The pulverizability decreases, leading to a decrease in productivity.

[0091] By providing at least one peak in each of the two molecular weight regions of the toner, the DSC maximum endothermic peak temperature of the toner is 60 to 100 ° C and the toner has a specific circularity. Synergistically, the effect of further improving the fixing property and the developing property appears.

By providing such a molecular weight distribution, not only the fixing property is further improved, but also the anti-offset property is improved, and the effect of the wax can be maximized. Furthermore, since the dispersibility is also improved, the generation of free raw materials is small, and the transferability and the chargeability are not hindered, so that the effect of the transferability and the developability by increasing the circularity can be more remarkably exhibited. it can.

In order for the toner of the present invention to have the above-mentioned molecular weight distribution, the binder resin component used in the present invention comprises T
In the molecular weight distribution of the HF soluble component measured by GPC, a low molecular weight polymer having at least one peak in a molecular weight region of 3,000 to 50,000, and a molecular weight of 5
It is preferable to be composed of a high molecular weight polymer having at least one peak or shoulder in the range of 0000 to 10,000,000.

These binder resin components may be mixed and dispersed with a wax component in advance in producing a toner. In particular, a method in which the wax component and the high molecular weight polymer are preliminarily dissolved in a solvent during the production of the binder, and then mixed with the low molecular weight polymer solution is preferable. By mixing the wax component and the high molecular weight component in advance, the phase separation in the micro region is reduced, the high molecular weight component is not re-aggregated, and a good dispersion state with the low molecular weight component can be obtained.

In the present invention, the toner or the binder resin
The molecular weight distribution by GPC using THF (tetrahydrofuran) as a solvent is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and THF was used as a solvent at this temperature.
At a flow rate of 1 ml / min.
Measure by injecting 0 μl. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, Tosoh Corporation or Showa Denko KK having a molecular weight of about 10 ² to 10 ⁷ is used, and it is appropriate to use a standard polystyrene sample of at least about 10 points. . 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 KF-801, 802, 80 manufactured by Showa Denko KK
3,804,805,806,807,800P or TSKgelG1000H (H
_{XL), G2000H (H XL)} , G3000H (H XL),
_{G4000H (H XL), G5000H (} H XL), G60
00H (H _XL ), G7000H (H _XL ), TSKgua
rdcolumn can be mentioned.

A sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours,
Shake well and mix well with THF (until the sample is no longer united) and let sit for at least 12 hours. At this time, THF
The time for which the sample is left inside is set to 24 hours or more. Thereafter, the sample processing filter (pore size 0.
45 to 0.5 μm, for example, Mysholidisk H-25
-5, manufactured by Tosoh Corporation, and manufactured by Exiclodisc 25CR Germanic Science Japan) can be used as a GPC measurement sample. The sample concentration is
The resin component is adjusted to be 0.5 to 5 mg / ml.

Examples of the binder resin used in the present invention include vinyl resins, phenol resins, phenol resins modified with natural resins, maleic acid resins modified with natural resins, acrylic resins, methacryl resins, polyvinyl acetates, silicone resins, polyester resins, Examples include polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaroindene resin, and petroleum resin. Among them, vinyl resins and polyester resins are preferable in terms of chargeability and fixability.

As the vinyl resin, for example, styrene;
o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene,
p-ethylstyrene, 2,4-dimethylstyrene, p-
n-butylstyrene, p-tert-butylstyrene,
Styrene derivatives such as pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene;
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 esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate Acrylates such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone ,
Vinyl ketones such as vinylhexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes;
Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; α,
Examples include esters of β-unsaturated acids and diesters of dibasic acids. These vinyl monomers can be used alone or
One or more are used.

Of these, a combination of monomers that results in a styrene copolymer or a styrene-acrylic copolymer is preferred.

Further, if necessary, a polymer or a copolymer cross-linked with a cross-linkable monomer as exemplified below may be used.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene; examples of the diacrylate compound linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds Examples of the acrylate include methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate,
Tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and the above compounds in which the acrylate is replaced with methacrylate; including an aromatic group and an ether bond Examples of chain-linked diacrylate compounds include polyoxyethylene (2) -2,2
-Bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-
(Hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; polyester-type diacrylates include, for example, the trade name MANDA (Nippon Kayaku).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compound with methacrylate; Triallyl cyanurate and triallyl trimellitate;

These cross-linking agents may be used in combination with 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.

Among these crosslinkable monomers, those which are preferably used from the viewpoint of fixing properties and offset resistance to the resin for toner include aromatic divinyl compounds (particularly divinylbenzene), chains containing an aromatic group and an ether bond. Diacrylate compounds tied together.

In the present invention, a homopolymer or copolymer of a vinyl monomer, polyester, polyurethane, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, An aromatic petroleum resin or the like can be used by mixing it with the binder resin described above, if necessary.

When two or more resins are mixed and used as a binder resin, as a more preferred form, those having different molecular weights are preferably mixed at an appropriate ratio.

The glass transition temperature of the binder resin is preferably 4
The temperature is 5 to 80C, more preferably 55 to 70C, 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.
It is preferred that

As a method for synthesizing a binder resin comprising a vinyl polymer or a copolymer, polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization 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 due to the nature of the monomer.

As the binder resin, the following polyester resins are also preferable.

The polyester resin contained 45 to 55 of all components.
mol% is the alcohol component, 55 to 45 mol%
Is an acid component.

Examples of the alcohol component include 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, a bisphenol derivative represented by the following formula (B);

[0114]

Embedded image

Diols represented by the formula (C):

[0116]

Embedded image Examples include polyhydric alcohols such as glycerin, sorbit, and sorbitan.

Examples of the divalent carboxylic acid containing 50 mol% or more of the total acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; succinic acid, adipic acid, sebacine Acids, anhydrides of alkyl dicarboxylic acids such as azelaic acid, and succinic acids or anhydrides thereof further substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms; fumaric acid, maleic acid, citraconic acid, itaconic acid; Unsaturated dicarboxylic acids or anhydrides thereof, and the like, and trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and anhydrides thereof.

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

This is because the toner for fixing with a heat roller using the polyester resin obtained from the acid component and the 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, and the OH value is preferably 50 mg KOH / g.
Or less, more preferably 30 mgKOH / g or less. This is because the environmental dependence of the charging characteristics of the toner increases as the number of terminal groups in the molecular chain increases.

The glass transition temperature of the polyester resin is preferably from 50 to 75 ° C., more preferably from 55 to 65 ° C., and the number average molecular weight (Mn) is preferably from 1,50.
0-50,000, more preferably 2,000-20,
000, and the weight average molecular weight (Mw) is preferably 6,000 to 100,000, more preferably 10,000.
It is preferably from 00 to 90,000.

That is, according to the study of the present inventors, in the toner manufactured by the pulverization method, the transfer rate at the time of transferring the toner image from the photoreceptor to the transfer material is improved, so that the waste toner is generated. In order to achieve good low-temperature fixability and high developability, the toner pulverized by a manufacturing device combining a specific pulverizer and a specific classifier has the specific circularity described above, The toner has a maximum endothermic peak temperature of 60 to 100 on a DSC curve measured by a differential scanning calorimeter.
° C, preferably GPC of the THF-soluble component of the toner.
3,000 in the molecular weight distribution measured by
Having at least one peak in the region of ~ 50,000
It is important to have at least one peak or shoulder in the region of molecular weight 50,000-10,000,000.

In the toner of the present invention, a charge control agent can be used if necessary in order to further stabilize the chargeability. The charge control agent is used in an amount of 0.1 per 100 parts by mass of the binder resin.
It is preferable to use 1 to 10 parts by mass, preferably 1 to 5 parts by mass.

The following are mentioned as charge control agents.

As a negative charge controlling agent for controlling the toner to negative charge, for example, an organometallic complex or a chelate compound is effective. Examples thereof include a monoazo metal complex, a metal complex of an aromatic hydroxycarboxylic acid, and a metal complex of an aromatic dicarboxylic acid. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides or esters thereof, and phenol derivatives of bisphenol.

Examples of the positive charge controlling agent for controlling the toner to have a positive charge include nigrosine, nigrosine derivatives, triphenylmethane compounds, and organic quaternary ammonium salts.

When the toner of the present invention is used as a magnetic toner, the magnetic materials contained in the magnetic toner include iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co, Ni Or a metal such as Al, Co, Cu,
Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

Specifically, as the magnetic material,
Iron (Fe_ThreeO_Four), Iron sesquioxide (γ-Fe_TwoO_Three),iron oxide
Zinc (ZnFe_TwoO_Four), Yttrium iron oxide (Y_ThreeFe_Five
O₁₂), Cadmium iron oxide (CdFe_TwoO_Four), Iron oxide gas
Dolinium (Gd_ThreeFe_FiveO₁₂), Copper iron oxide (CuFe_Two
O_Four), Lead iron oxide (PbFe₁₂O₁₉), Nickel iron oxide
(NiFe_TwoO_Four), Iron neodymium oxide (NdFe_TwoO_Three),
Barium oxide (BaFe)₁₂O₁₉), Iron oxide magnesium
(MgFe_TwoO_Four), Iron manganese oxide (MnFe)
_TwoO_Four), Iron oxide lanthanum (LaFeO)_Three), Iron powder (F
e), cobalt powder (Co), nickel powder (Ni), etc.
I can do it. The above magnetic materials can be used alone or in combination of two or more.
Use in combination. A particularly preferred magnetic material is ferric oxide
Or a fine powder of γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.05 to
At 2 μm, the magnetic properties at 795.8 kA / m applied 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 a remanent magnetization of ^{2 to 20} Am ² / kg are preferable.

The magnetic substance 1 was added to 100 parts by mass of the binder resin.
It is preferable to use 0 to 200 parts by mass, preferably 20 to 150 parts by mass.

As the nonmagnetic colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used.
For example, examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara, phthalocyanine blue, and indanthrene blue. These are 0.1 to 100 parts by mass of the binder resin.
The addition amount of 20 parts by mass, preferably 1 to 10 parts by mass is good. Similarly, dyes are used, for example, anthraquinone dyes, xanthene dyes, methine dyes,
The addition amount is 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the binder resin.

A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine silica powder such as wet-process silica and dry-process silica, fine titanium oxide, fine alumina powder, and silane compounds thereof.
Titanium coupling agents, treated silica surface-treated with silicone oil, etc., as inorganic fine powder,
Oxides such as zinc oxide and tin oxide; double oxides such as strontium titanate, barium titanate, calcium titanate, strontium zirconate and calcium zirconate; and carbonate compounds such as calcium carbonate and magnesium carbonate.

Preferred fluidity improvers are fine powders produced by the vapor phase oxidation of silicon halides, and are so-called dry silica or fumed silica. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this production process, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide. They are also included. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

Examples of commercially available fine silica powder produced by the vapor phase oxidation of silicon halides include those commercially available under the following trade names, for example.

AEROSIL (Aerosil Japan) 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 N20 V15 WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, a treated silica fine powder obtained by hydrophobizing silica fine powder generated by vapor-phase oxidation of the silicon halide compound is more preferable. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method for imparting hydrophobicity is provided by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

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

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by mass of the fluidity improver with respect to 00 parts by mass,
Preferably, 0.1 to 4 parts by mass is used.

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

FIG. 1 is an example of a flowchart showing the outline of the method for producing a toner of the present invention. As shown in the flowchart, the manufacturing method of the present invention does not require a classification step before the pulverizing treatment, and the pulverizing step and the classification step are performed in one pass.

In the method for producing a toner of the present invention, a mixture containing at least a binder resin, a colorant and a wax is melt-kneaded, and the obtained kneaded material is cooled. The obtained coarsely pulverized product is used as a powder raw material. Then, first, a rotor which is a rotating body having a predetermined amount of the pulverized raw material attached to at least the center rotating shaft, and a stator which is arranged around the rotor while keeping a constant interval from the rotor surface. By introducing into a mechanical crusher that is configured so that an annular space formed by maintaining the distance and having an airtight state, and rotating the rotor of the mechanical crusher at a high speed. Finely pulverize the object. Next, the finely pulverized raw material is introduced into a classification step and classified to obtain a classified product which is a toner raw material composed of a group of particles having a preferable 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 a classification means. For example, when a three-division airflow classifier is used, the powder material is at least a fine powder,
Classified into three types: medium powder and coarse powder. In the classifying step using such a classifier, a coarse powder composed of a group of particles having a particle size larger than a preferred particle size and an ultrafine powder composed of a group of particles having a particle size smaller than a specified particle size are removed, and the medium powder is formed of the inorganic fine powder. After being mixed with the body and an external additive such as hydrophobic colloidal silica, it is used as a toner.

The fine powder composed of particles having a particle size smaller than the preferred particle size classified in the above-mentioned classification step is generally subjected to a melt-kneading step for producing a powdery raw material composed of a toner material introduced into the pulverization step. To be reused or discarded. Also, ultrafine powder having a smaller particle diameter than the above fine powder and slightly generated in the pulverizing step and the classifying step is similarly supplied to the melt-kneading step and reused or discarded.

FIG. 2 shows an example of an apparatus system to which the method for producing a toner of the present invention is applied, and the present invention will be described more specifically based on this. As a powder raw material as a toner raw material introduced into this apparatus system, a colored resin particle powder containing at least a binder resin, a colorant and a wax is used. A mixture composed of a mixture of a colorant, a wax and the like is melt-kneaded, the obtained kneaded product is cooled, and the cooled product is roughly pulverized by a pulverizing means.

In this apparatus system, a predetermined amount of a pulverized raw material serving as a toner powder raw material is first introduced into a mechanical pulverizer 301 as a pulverizing means via a first constant supply device 315. The introduced pulverized raw material is instantaneously pulverized by the mechanical pulverizer 301 and is introduced into the second constant feeder 2 via the collection cyclone 229. Next, it is supplied into the multi-split airflow classifier 1 as a classifying means via the vibrating feeder 3 and further through the raw material supply nozzle 16.

In this apparatus system, the first fixed-quantity feeder 315 is provided with a mechanical pulverizer 301 as a pulverizing means.
The relationship between the predetermined amount introduced into the second constant feeder 2 and the predetermined amount introduced into the multi-split airflow type classifier 1 as the classification means from the second constant supply device 2 to the mechanical pulverizer 301 from the first constant supply device 315 Assuming that the predetermined amount to be introduced is 1, the predetermined amount to be introduced from the second fixed-quantity feeder 2 to the multi-split airflow classifier 1 is preferably 0.7 to 1.7, more preferably 0.7 to 1.7. And more preferably from 1.0 to 1.2 in terms of toner productivity and production efficiency.

Normally, the air-flow classifier of the present invention is used by connecting mutual devices by a communication means such as a pipe, and is incorporated in an apparatus system. FIG. 2 shows a preferred example of such an apparatus system. The integrated device system shown in FIG. 2 includes a multi-divided classifier 1 (classifier shown in FIG. 6),
The second fixed-quantity feeder 2, the vibration feeder 3, the collecting cyclone 4, the collecting cyclone 5, and the collecting cyclone 6 are connected by communication means.

In this system, the powder is fed into the quantitative feeder 2 by an appropriate means, and then introduced into the three-division classifier 1 through the vibrating feeder 3 by the raw material supply nozzle 16. For introduction, 10-3
The powder is introduced into the classifier 1 at a flow rate of 50 m / s. Since the size of the classifying chamber of the three-segment classifier 1 is usually [10 to 50 cm] × [10 to 50 cm], the powder is classified into three or more types of particles in an instant of 0.1 to 0.01 s or less. I can do it. Then, the particles are classified into large particles (coarse particles), intermediate particles, and small particles by the three-division classifier 1. Thereafter, the large particles pass through the discharge conduit 11a, are sent to the collection cyclone 6, and are returned to the mechanical grinder 301. The intermediate particles are discharged out of the system via the discharge conduit 12a, collected by the collection cyclone 5, and collected as toner. The small particles are discharged out of the system via the discharge conduit 13a, collected by the collection cyclone 4, and supplied to a melt-kneading process for producing a powder material composed of a toner material, and are reused, or Discarded. Capture cyclone 4,
5 and 6 can also function as suction pressure reducing means for sucking and introducing the powder into the classification chamber via the raw material supply nozzle 16. In addition, it is preferable that the large particles to be classified at this time are re-introduced into the first quantitative feeder 315, mixed into the powder raw material, and pulverized again by the mechanical pulverizer 301.

The re-introduction amount of large particles (coarse particles) re-introduced from the multi-split air classifier 1 to the mechanical pulverizer 301 depends on the mass of the finely pulverized product supplied from the second quantitative feeder 2. It is preferably 0 to 10.0% by mass, more preferably 0 to 5.0% by mass, based on the toner.
If the reintroduction amount of large particles (coarse particles) reintroduced from the multi-split air classifier 1 into the mechanical pulverizer 301 exceeds 10.0% by mass, the dust concentration in the mechanical pulverizer 301 increases. In addition, the load on the apparatus itself is increased, and at the same time, the toner is excessively pulverized at the time of pulverization.

In this apparatus system, the particle size of the powder raw material is 95 mass% or more in an 18 mesh pass (ASTME-11-61) and 100 mesh on (ASTM).
E-11-61) is preferably 90% by mass or more.

In order to obtain a toner having a sharp particle size distribution having a weight average particle size of 5 to 12 μm in this apparatus system, the weight average particle size of the finely pulverized material pulverized by a mechanical pulverizer is required. 4 to 12 μm, 4.0 μm or less is 70% by number or less, further 65% by number or less, 10.1 μm
m or more is preferably 40% by volume or less, more preferably 35% by volume or less. In addition, the particle size of the classified medium powder has a weight average particle size of 5 to 12 μm, 4.0 μm or less is 40% by number or less,
35% by volume or less and 35% by volume of 10.1 μm or more
The content is preferably 30% by volume or less.

In the above-described apparatus system to which the method for producing a toner according to the present invention is applied, the pulverizing step and the classifying step can be performed in one pass without requiring the first classifying step before the pulverizing treatment.

A mechanical pulverizer preferably used as a pulverizing means used in the toner production method of the present invention will be described. Examples of the mechanical pulverizer include a pulverizer KTM and Kryptron manufactured by Kawasaki Heavy Industries, Ltd., and a turbo mill manufactured by Turbo Kogyo Co., Ltd. These apparatuses can be used as they are or after being appropriately improved. preferable.

In the present invention, FIG.
It is preferable to use a mechanical pulverizer as shown in FIGS. 4 and 5 because the pulverization process of the powder raw material can be easily performed and the efficiency can be improved.

Hereinafter, the mechanical pulverizer shown in FIGS. 3, 4 and 5 will be described. FIG. 3 shows a schematic cross-sectional view of an example of a mechanical crusher used in the present invention,
FIG. 4 is a schematic sectional view taken along the line DD ′ in FIG. 3, and FIG. 5 is a perspective view of the rotor 314 shown in FIG. The apparatus includes a casing 313, a jacket 316, and a distributor 22 as shown in FIG.
0, a rotor 314 having a large number of grooves formed on a high-speed rotating surface formed of a rotating body attached to a center rotating shaft 312 in a casing 313, and arranged at an outer periphery of the rotor 314 at a constant interval. A stator 310 having a large number of grooves on its surface, a raw material input port 311 for introducing a raw material to be processed, and a raw material discharge port 302 for discharging processed powder. ing.

The pulverizing operation of the mechanical pulverizer constructed as described above is performed, for example, as follows.

That is, when a predetermined amount of powder raw material is introduced from the powder inlet 311 of the mechanical pulverizer shown in FIG. 3, the particles are introduced into the pulverization processing chamber and are rotated at a high speed in the pulverization processing chamber. Rotor 314 having a large number of grooves on the surface
And the stator 310 having a large number of grooves formed on the surface thereof, and the instantaneous pulverization caused by a number of super-high-speed vortices generated behind the high-frequency vortex and the high-frequency pressure vibration generated thereby. . After that, it is discharged through the raw material discharge port 302. The air (air) carrying the toner particles passes through the pulverization processing chamber, and is supplied to the raw material discharge port 302, the pipe 219, the collection cyclone 229, and the bag filter 2.
22, and is discharged out of the system of the apparatus system through the suction filter 224. In the present invention, the pulverization of the powdery raw material is performed in this manner, so that a desired pulverization treatment can be easily performed without increasing fine powder and coarse powder.

When the pulverized raw material is pulverized by a mechanical pulverizer, it is preferable that the cool air generating means 321 sends cool air into the mechanical pulverizer together with the powder material. Furthermore,
The temperature of the cold air is preferably 0 to -18 ° C. Further, as a cooling means inside the mechanical pulverizer main body, the mechanical pulverizer has a structure having a jacket structure 316,
It is preferable to pass cooling water (preferably an antifreeze such as ethylene glycol). Further, the room temperature T1 in the spiral chamber 212 communicating with the powder introduction port in the mechanical pulverizer is reduced to 0 ° C. or lower, more preferably −5 to −15 ° C., and still more preferably −7 by the above-described cool air device and jacket structure. ~ -12 ° C
Is preferred from the viewpoint of toner productivity. The room temperature T1 of the vortex chamber in the crusher is 0 ° C. or less, more preferably −
By setting the temperature to 5 to -15 ° C, and more preferably to -7 to -12 ° C, it is possible to suppress deterioration of the surface of the toner due to heat, and it is possible to efficiently pulverize the raw material. If the room temperature T1 of the spiral chamber in the pulverizer exceeds 0 ° C., it is not preferable from the viewpoint of toner productivity because the surface of the toner is liable to be deteriorated due to heat during the pulverization and the internal fusing is easily caused. If the room temperature T1 of the spiral chamber in the crusher is to be operated at a temperature lower than −15 ° C., the refrigerant (alternative Freon) used in the cold air generating means 321 must be changed to Freon.

At present, elimination of CFCs is being promoted from the viewpoint of protection of the ozone layer. It is not preferable to use chlorofluorocarbon as the refrigerant of the cold air generating means 321 from the viewpoint of global environmental problems.

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

When the pulverized raw material is pulverized by a mechanical pulverizer, the room temperature T1 of the spiral chamber 212 of the mechanical pulverizer and the rear chamber 3 are reduced.
The temperature difference ΔT (T2−T1) of the room temperature T2 of 20 to 30 to 8
The temperature is preferably 0 ° C, more preferably 35 to 75.
C., more preferably from 37 to 72 ° C., the surface of the toner can be prevented from being deteriorated due to heat, and the raw material can be efficiently pulverized. ΔT between the temperature T1 (inlet temperature) and the temperature T2 (outlet temperature) of the mechanical crusher is 3
If the temperature is lower than 0 ° C., a short path may occur without being pulverized, which is not preferable in terms of toner performance. On the other hand, if the temperature is higher than 80 ° C., the toner may be excessively pulverized at the time of pulverization, and the surface of the toner may be deteriorated by heat or may be easily fused in the apparatus.

When the pulverized raw material is pulverized by a mechanical pulverizer, the room temperature T1 of the spiral chamber 212 of the mechanical pulverizer is set at 0 ° C.
From the viewpoint of toner productivity, it is preferable that the temperature is lower by 60 to 75 ° C. than the glass transition point (Tg) of the binder resin. By setting the room temperature T1 of the spiral chamber 212 of the mechanical pulverizer to 0 ° C. or lower and 60 to 75 ° C. lower than Tg, it is possible to suppress the surface deterioration of the toner due to heat, and to efficiently pulverize the raw material. Can be. The room temperature T2 of the rear chamber 320 of the mechanical crusher is T
It is preferably 5 to 30 ° C, more preferably 10 to 20 ° C lower than g. By lowering the room temperature T2 of the rear chamber 320 of the mechanical pulverizer by 5 to 30 ° C. lower than Tg, it is possible to suppress the deterioration of the surface of the toner due to heat, and to pulverize the pulverized raw material efficiently.

Further, the peripheral speed of the tip of the rotating rotor 314 is preferably 80 to 180 m / s, more preferably 90 to 170 m / s, and further preferably 100 to 180 m / s.
-160 m / s is preferable from the viewpoint of toner productivity. The peripheral speed of the rotating rotor 314 is set to 80 to 180.
By adjusting the m / s to 90 m / s, more preferably 90 to 170 m / s, and more preferably 100 to 160 m / s, insufficient pulverization and excessive pulverization of the toner can be suppressed, and the pulverized raw material can be efficiently pulverized. If the peripheral speed of the rotor is lower than 80 m / s, it is not preferable from the viewpoint of toner performance because a short path is easily generated without being pulverized. When the peripheral speed of the rotor 314 is higher than 180 m / s, the load on the apparatus itself is increased, and at the same time, the toner is excessively pulverized at the time of pulverization, so that the surface of the toner is easily deteriorated by heat and the inside of the apparatus is fused. This is not preferable from the viewpoint.

The minimum distance between the rotor 314 and the stator 310 is preferably 0.5 to 10.0 mm, more preferably 1.0 to 5.0 mm, and still more preferably 1.0 to 5.0 mm. It is preferably 3.0 mm. Rotor 3
0.5 to 10.0 m between the stator 14 and the stator 310
m, more preferably 1.0 to 5.0 mm, and still more preferably 1.0 to 3.0 mm, it is possible to suppress insufficient pulverization of the toner and excessive pulverization, and to pulverize the pulverized raw material efficiently. it can. If the distance between the rotor 314 and the stator 310 is larger than 10.0 mm, it is not preferable in terms of toner performance because a short path is easily generated without being pulverized. If 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 toner is over-pulverized at the time of pulverization, and the surface of the toner is likely to deteriorate due to heat and fuse in the apparatus. Therefore, it is not preferable from the viewpoint of toner productivity.

Since the pulverization method of the present invention does not require the first classification step before the pulverization step, the toner is made finer, so that the electrostatic aggregation between the particles is increased, and the toner is originally sent to the second classification means. By re-circulating the toner to the first classifying means, over-pulverized fine powder and ultra-fine powder are not generated.
Furthermore, in addition to a simple configuration, a large amount of air is not required to pulverize the raw material, so that power consumption is low and energy cost can be reduced.

Next, an air flow classifier preferably used as a classifying means constituting the toner production method of the present invention will be described.

As an example of a preferred multi-split air classifier used in the present invention, an apparatus of the type shown in FIG. 6 (cross-sectional view) will be exemplified as a specific example.

In FIG. 6, the side wall 22 and the G block 2
3 forms part of the classification chamber, the classification edge blocks 24 and 25 are provided with classification edges 17 and 18. The installation position of the G block 23 can be slid right and left. Further, the classification edges 17 and 18 correspond to the shaft 17a.
And 18a can be rotated, and the classification edge can be rotated to change the classification edge tip position.
Each of the classifying edge blocks 24 and 25 can be slid right and left, and accordingly, the respective knife-edge classifying edges 17 and 18 also slide right and left. The classification area 30 of the classification chamber 32 is divided into three by the classification edges 17 and 18.

Raw material supply port 40 for introducing raw material powder
At the rear end of the material supply nozzle 16, a high pressure air supply nozzle 41 and a material powder introduction nozzle 42 at the rear end of the material supply nozzle 16, and an opening in the classifying chamber 32. A raw material supply nozzle 16 is provided on the right side of the side wall 22,
The Coanda block 26 is provided so as to draw a long elliptical arc in the direction in which the lower tangent of the raw material supply nozzle 16 extends. The left block 27 of the classifying chamber 32 has a knife-edge type inlet edge 19 on the right side of the classifying chamber 32, and furthermore, on the left side of the classifying chamber 32, the inlet pipe 1 opening to the classifying chamber 32.
4 and 15 are provided. Further, as shown in FIG. 2, first and second gas introduction adjusting means 20, 21 such as a damper, and a static pressure gauge 28 are provided in the intake pipes 14 and 15, respectively.
And a static pressure gauge 29 are provided.

The positions of the classification edges 17, 18, the G block 23, and the inlet edge 19 are adjusted according to the type and desired particle size of the toner to be classified.

On the upper surface of the classifying chamber 32, the outlets 11, 1 opening into the classifying chamber corresponding to the respective dividing areas.
2 and 13, and communication means such as a pipe is connected to the discharge ports 11, 12 and 13, and each of them may be provided with an opening / closing means such as a valve means.

The raw material supply nozzle 16 is composed of a right-angled cylinder and a pyramidal cylinder. The ratio of the inner diameter of the right-angled cylinder to the inner diameter of the narrowest part of the pyramidal cylinder is 20: 1 to 1: 1, preferably 10: 1. : 1
If the ratio is set to 2: 1 from, a good introduction speed can be obtained.

The classification operation in the multi-division classification region configured as described above is performed, for example, as follows. That is, the pressure in the classification chamber is reduced through at least one of the discharge ports 11, 12, and 13, and the air flow flowing by the reduced pressure and the high-pressure air supply nozzle 41 in the raw material supply nozzle 16 having an opening in the classification chamber are injected. Due to the ejector effect of compressed air, the powder is ejected into the classifying chamber through the raw material supply nozzle 16 at a flow rate of preferably 10 to 350 m / s, and dispersed.

The particles in the powder introduced into the classifying 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 air flowing in at that time. Depending on the particle size and the magnitude of the inertial force, large particles (coarse particles) are outside the airflow, ie, 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 a third fraction inside the classification edge 17, the classified large particles are discharged from the outlet 11, the intermediate classified particles are discharged from the outlet 12, and the classified small particles are discharged. Are respectively discharged from the discharge ports 13.

In the above-described 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 into the classification chamber 32. Further, the classification point is affected by the suction flow rate of the classification airflow, the powder ejection speed from the raw material supply nozzle 16, and the like.

In the toner production method and production system of the present invention, by controlling the pulverization and classification conditions, a toner having a sharp particle size distribution with a weight average particle diameter of 5 to 12 μm is efficiently produced. be able to.

The toner production method of the present invention can be preferably used for producing toner particles used for developing an electrostatic image. To prepare an electrostatic image developing toner, a mixture containing at least a binder resin, a colorant and a wax is used as a material. In addition, if necessary, a magnetic powder, a charge control agent, and other additives are used. Are used. After thoroughly mixing these materials with a mixer such as a Henschel mixer or a ball mill, a roll,
Using a hot kneader such as a kneader and an extruder, melted, kneaded and kneaded to make the resins compatible with each other, disperse or dissolve the pigment or dye, and after cooling and solidifying,
The toner can be obtained by performing pulverization and classification. In the present invention, the apparatus system having the above-described configuration is used in the pulverization step and the classification step.

For example, as a mixer, Henschel mixer (manufactured by Mitsui Mining); super mixer (manufactured by Kawata); ribocorn (manufactured by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige mixer (manufactured by Matsubo), and kneading machines include KRC kneader (manufactured by Kurimoto Iron Works); bus co-kneader (manufactured by Buss); TEM Mold extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); knee Decks (manufactured by Mitsui Mining Co., Ltd.); MS-type pressurized kneader, nider ruder (manufactured by Moriyama Seisakusho); Banbury mixer (manufactured by Kobe) Tokorosha, Ltd.) and the like. Examples of the pulverizer include a counter jet mill, a micron jet, an inomaizer (manufactured by Hosokawa Micron); an IDS-type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic), a cross jet mill (manufactured by Kurimoto Tekkosho); SK Jet ・
Oh Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); and Turbo Mill (manufactured by Turbo Kogyo). Classifiers include Classile, Micron Classifier, Spedd Classifier (Seishin Enterprise); Turbo Classifier (Nissin Engineering); Micron separator, Turboflex (ATP), TSP separator (Hosokawa Micron) Elbow jet (manufactured by Nippon Steel Mining), dispersion separator (manufactured by Nippon Pneumatic), and YM microcut (manufactured by Yasukawa Shoji). Ultrasonic (Koei Sangyo Co., Ltd.); Resona Seeb, Gyro Shifter (Tokuju Kosakusho Mori); Vibrasonic System (Dalton Co., Ltd.); Sonic Clean (Shinto) Turbo Screener (manufactured by Turbo Industries); Microshifter (manufactured by Makino Sangyo); circular vibrating sieve.

[0181]

Next, the present invention will be described in more detail with reference to examples and comparative examples of the present invention, but this does not limit the present invention in any way. “Parts” means “parts by mass”.

(Polymer Synthesis Example 1) 300 parts of xylene was charged into a four-necked flask, and the inside of the vessel was sufficiently purged with nitrogen while stirring. Then, the mixture was heated and refluxed. A mixture of 0.8 parts, 22 parts of n-butyl acrylate, 9.2 parts of monobutyl maleate, and 1.8 parts of di-tert-butyl peroxide was added dropwise over 4 hours, and the mixture was held for 2 hours and polymerized. Was completed and the solvent was removed to obtain a polymer L1. GPC measurement of this polymer L1 showed a peak molecular weight of 15,000.

(Polymer Synthesis Example 2) 180 parts of degassed water and 20 parts of a 2% by weight aqueous solution of polyvinyl alcohol were charged into a four-necked flask, and then 74.9 parts of styrene, 20 parts of n-butyl acrylate, A mixed solution of 5.0 parts of monobutyl maleate and 0.2 parts of 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane was added, and stirred to form a suspension. After sufficiently replacing the inside of the flask with nitrogen, the temperature was raised to 90 ° C. to initiate polymerization. The polymerization was completed by maintaining the same temperature for 24 hours to obtain a polymer H1.
Thereafter, the polymer H1 was separated by filtration, dried, and then subjected to GPC measurement to find that the peak molecular weight was 800000.

[Synthesis Example of Binder Resin] Polymer L1 and polymer H
1 in a 70:30 mass ratio in a xylene solution,
Binder resin 1 was obtained.

[Production Example 1 of Crushed Toner] As a binder resin, 100 parts of the above-mentioned binder resin 1 was prepared by using a magnetic iron oxide (average particle diameter: 0.20 μm, 795.8 kA / m magnetic field H).
c: 9.2 kA / m, σs: 82 Am ² / kg, σr:
90 parts of 11.5 Am ² / kg), 3 parts of monoazo metal complex (negative charge controlling agent), paraffin wax W1 shown in Table 1 (maximum endothermic peak temperature 75 ° C., penetration (25 ° C.))
7.0 parts, 3 parts of the number average molecular weight (polyethylene equivalent: 390) measured by GPC were previously uniformly mixed,
This was melt-kneaded with a twin-screw extruder heated to 130 ° C. The obtained kneaded material is cooled and coarsely pulverized by a hammer mill to obtain a powder material A which is a powder material for toner production.
(Coarse pulverized product) was obtained.

[Production Example 2 of Crumbled Toner] As a wax component, Fischer-Tropsch wax W2 (maximum endothermic peak temperature 73 ° C., penetration (25 ° C.) 6.0 mm, G
A powder raw material B (coarse pulverized product) was obtained in the same manner as in Production Example 1 of the pulverized toner, except that the number average molecular weight (polyethylene equivalent) measured by PC was 360).

[Production Example 3 of Crushed Toner] As a wax component, Fischer-Tropsch wax W3 (maximum endothermic peak temperature 89 ° C., penetration (25 ° C.) 3.0 mm, G
A powder raw material C (coarse pulverized product) was obtained in the same manner as in Production Example 1 of the toner pulverized substance, except that the number average molecular weight (in terms of polyethylene) of 580 measured by PC was used.

[Production Example 4 of Crushed Toner] As a wax component, polyethylene wax W4 (maximum endothermic peak temperature 94 ° C., penetration (25 ° C.) 2.0 mm), number average molecular weight measured by GPC (polyethylene equivalent) 630)
In the same manner as in Production Example 1 of the coarsely crushed toner, except that the above was used, a powder raw material D (crudely crushed material) was obtained.

[Production Example 5 of Crumbled Toner] As a wax component, polyethylene wax W5 (maximum endothermic peak temperature: 76 ° C., penetration (25 ° C.): 6.5 mm), number average molecular weight measured by GPC (in terms of polyethylene) 380)
In the same manner as in Production Example 1 of the coarsely crushed toner, except that the powder raw material E was obtained.

[Production Example 6 of Crushed Toner] As a wax component, alcohol wax W6 (maximum endothermic peak temperature: 68 ° C., penetration (25 ° C.): 7.0 mm), number average molecular weight measured by GPC (polyethylene equivalent) 290) to obtain a powder raw material F (coarse crushed product) in the same manner as in Production Example 1 of the crushed toner.

[Production Example 7 of Crumbled Toner] As a wax component, alcohol wax W7 (maximum endothermic peak temperature 93 ° C., penetration (25 ° C.) 3.0 mm), number average molecular weight measured by GPC (polyethylene equivalent) Powder raw material G (coarse pulverized material) was obtained in the same manner as in Production Example 1 of the coarsely pulverized toner except for using the above (410).

[Production Example 8 of Crushed Toner] As a wax component, polyethylene wax W8 (maximum endothermic peak temperature 124 ° C., penetration (25 ° C.) 0.5 mm), number average molecular weight measured by GPC (in terms of polyethylene) 74
Powdered raw material H (coarse pulverized material) was obtained in the same manner as in Production Example 1 of the coarsely pulverized toner except that the value was 0).

[Production Example 9 of Crushed Toner] As wax component, polypropylene wax W9 (maximum endothermic peak temperature: 143 ° C., penetration (25 ° C.): 0.5 mm), number average molecular weight measured by GPC (polyethylene equivalent) 10
Powder raw material I (coarse pulverized material) was obtained in the same manner as in Production Example 1 of the coarsely pulverized toner material, except for using 10).

<Example 1> Powder raw material A was pulverized and classified by an apparatus system shown in FIG. Mechanical crusher 301
, A turbo mill T-250 manufactured by Turbo Kogyo Co., Ltd. was used, the interval between the rotor 314 and the stator 310 shown in FIG. 3 was 1.5 mm, and the peripheral speed of the rotor 314 was operated at 131 m / s.

In the present embodiment, the powdery raw material composed of the coarsely pulverized material is reduced to 40 kg /
h and was supplied to the mechanical pulverizer 301 and pulverized. The powder raw material pulverized by the mechanical pulverizer 301 is entrained by the suction air from the exhaust fan 224, and
It is collected at 29 and introduced into the second metering device 2.
At this time, the inlet temperature in the mechanical pulverizer was -10 ° C,
The outlet temperature was 46 ° C., and the temperature difference ΔT between the inlet temperature and the outlet temperature was 56 ° C. At this time, the finely pulverized product Aa-1 obtained by pulverization by the mechanical pulverizer 301 has a weight average diameter of 6.6 μm and particles having a particle diameter of 4.0 μm or less.
It had a sharp particle size distribution containing 6% by number and 3.1% by volume of particles having a particle size of 10.1 μm or more.

Next, the finely pulverized product Aa-1 obtained by pulverization by the mechanical pulverizer 301 is introduced into the second constant-volume feeder 2, and is fed through the vibrating feeder 3 and the raw material supply nozzle 16 to 44 kg. / H was introduced into the airflow classifier 1 having the configuration shown in FIG. In the air-flow classifier 1, the powder is classified into three kinds of particle sizes of a coarse powder, a medium powder, and a fine powder by utilizing the Coanda effect. At the time of introduction into the airflow classifier 1, the pressure in the classification chamber is reduced through at least one of the outlets 11, 12, and 13, and the airflow flowing through the raw material supply nozzle 16 having an opening in the classification chamber due to the reduced pressure. And compressed air injected from the high-pressure air supply nozzle 41. Introduced finely pulverized product, coarse powder,
The powder was classified into three types: medium powder Aa-2 and fine powder. Among the classified materials, the coarse powder was collected by the collection cyclone 6 and then fed to the mechanical pulverizer 301 described above at 2.0 kg / h.
And introduced again into the pulverizing step.

The medium powder Aa- classified in the above classification step
2 (classified product) has a weight average diameter of 6.8 μm, particles having a particle diameter of 4.0 μm or less are 20.2% by number, and a particle diameter of 1
It had a sharp particle size distribution containing 2.3% by volume of particles of 0.1 μm or more. At this time, the ratio (that is, the classification yield) of the amount of the finally obtained medium powder to the total amount of the charged powder raw materials was 85% by mass.

With respect to 100 parts of the powder Aa-2,
1.0 part of hydrophobic silica fine powder (BET 300 m ² / g) was externally added using a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain a toner for evaluation (A).

The circularity of the toner (A) was measured using FPIA-100.
0 (manufactured by Toa Medical Electronics Co., Ltd.), the toner (A) was 95.8 in terms of the number-based cumulative value of particles having a circularity of 0.900 or more among particles having a circle-equivalent diameter of 3 μm or more.
%, And particles having a circularity of 0.950 or more are contained in a cumulative value of 78.4% based on the number, and the cut ratio Z at this time is 1
2.1%. The relationship between the circularity and the weight average particle size satisfied the requirements of the present invention (see FIG. 12).

<Examples 2 to 7> Powder raw materials B to G were pulverized in the same manner as in Example 1 to obtain finely pulverized products B-1, C-1,
D-1, E-1, F-1, and G-1 were obtained. Thereafter, the powder was classified in the same manner as in Example 1, and the respective powders were classified into medium powders (classified products) B-2,
C-2, D-2, E-2, F-2 and G-2 were obtained.

Next, this medium powder (classified product) B-2, C-
2, D-2, E-2, F-2, and G-2 were externally added in the same manner as in Example 1, and the evaluation toners (i), (u), and
(E), (O), (K), (K).

Table 2 shows the particle size distribution, cut rate, and circularity of each evaluation toner. Each of the toners (i) to (g) satisfied the requirements of the present invention in the relationship between the circularity and the weight average particle diameter (see FIG. 12).

<Comparative Examples 1 and 2> Powder materials H and I were pulverized in the same manner as in Example 1 to obtain finely pulverized products H-1 and I, respectively.
-1 was obtained. Thereafter, classification was performed in the same manner as in Example 1 to obtain medium powders (classified products) H-2 and I-2, respectively.

Next, these medium powders (classified products) H-2 and I-2 were externally added in the same manner as in Example 1 to obtain evaluation toners (se) and (so), respectively.

Table 2 shows the particle size distribution, cut rate, and circularity of each evaluation toner. The toners (se) and (so) satisfied the requirements of the present invention in the relationship between the circularity and the weight average particle diameter (see FIG. 12).

Example 8 Powder material A was ground in the same manner as in Example 1 except that the peripheral speed in the fine grinding step was changed to 143 m / s. The outlet temperature was 48 ° C., and the inlet temperature and the outlet The temperature difference ΔT between the temperatures was 58 ° C. At this time, a finely pulverized product A obtained by pulverizing with a mechanical pulverizer 301
b-1 has a weight average diameter of 5.5 μm and a particle diameter of 4.0.
45.5% by number of particles of μm or less, and particle size of 10.1μ
m or more contained 1.1% by volume.

Next, the finely pulverized product Ab-1 obtained by pulverization by the mechanical pulverizer 301 was classified in the same manner as in Example 1, and the classified medium powder Ab-2 (classified product) Has a particle size distribution in which the weight average particle size is 5.6 μm, the particles having a particle size of 4.0 μm or less are 34.5% by number, and the particles having a particle size of 10.1 μm or more are 0.5% by volume. Was. At this time, the ratio of the amount of the intermediate powder finally obtained to the total amount of the charged powder raw materials (that is, the classification yield) was 83% by mass.
Met.

With respect to 100 parts of the powder Ab-2,
1.2 parts of hydrophobic silica fine powder (BET 300 m ² / g) was externally added using a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain an evaluation toner (K).

In the toner (g), particles having a circularity of not less than 3 μm have a circularity of 0.900 or more and the number-based cumulative value is 97.7%, and the particles having a circularity of 0.950 or more are counted. It contained 82.6% as a reference cumulative value, and the cut ratio Z at this time was 12.8%. The toner (g) satisfied the requirements of the present invention in relation to the circularity and the weight average particle diameter (see FIG. 12).

Example 9 Powder material A was ground in the same manner as in Example 1 except that the peripheral speed in the fine grinding step was changed to 104 m / s. The outlet temperature was 38 ° C., and the inlet temperature and outlet The temperature difference ΔT between the temperatures was 48 ° C. At this time, a finely pulverized product A obtained by pulverizing with a mechanical pulverizer 301
c-1 has a weight average diameter of 9.0 μm and a particle diameter of 4.0.
34.5% by number of particles of μm or less, and particle size of 10.1μ
m or more contained 34.9% by volume.

Next, the finely pulverized product Ac-1 obtained by pulverization by the mechanical pulverizer 301 was classified in the same manner as in Example 1, and the classified medium powder Ac-2 (classified product) Has a weight average diameter of 9.1 μm, 5.1% by number of particles having a particle size of 4.0 μm or less, and 3 particles having a particle size of 10.1 μm or more.
It had a particle size distribution containing 2.6% by volume. At this time, the ratio of the amount of the finally obtained medium powder to the total amount of the charged powder raw materials (that is, the classification yield) was 80% by mass.
Met.

With respect to 100 parts of this medium powder Ac-2,
0.7 parts of hydrophobic silica fine powder (BET 300 m ² / g) was externally added by a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain a toner for evaluation (ke).

[0213] The toner (ke) includes particles having a circularity of 3 μm or more and a particle having a circularity of 0.900 or more in a number-based cumulative value of 92.5%, and a particle having a circularity of 0.950 or more. The content was 63.0% as a reference cumulative value, and the cut ratio Z at this time was 31.6%. The toner (K) satisfied the requirements of the present invention in relation to the circularity and the weight average particle diameter (see FIG. 12).

Example 10 Powder material A was ground in the same manner as in Example 1 except that the peripheral speed in the fine grinding step was changed to 95 m / s. The outlet temperature was 33 ° C., and the inlet temperature and the outlet The temperature difference ΔT between the temperatures was 43 ° C. At this time, a finely pulverized product A obtained by pulverizing with a mechanical pulverizer 301
d-1 has a weight average diameter of 10.5 μm and a particle diameter of 4.
34.0% by number of particles having a particle size of 0 μm or less and a particle size of 10.1
48.9% by volume of particles of μm or more were contained.

Next, the finely pulverized product Ad-1 obtained by pulverization by the mechanical pulverizer 301 was classified in the same manner as in Example 1, and the classified intermediate powder Ad-2 (classified product) Means that particles having a weight average diameter of 10.8 μm, particles having a particle diameter of 4.0 μm or less are 1.5 number%, and particles having a particle diameter of 10.1 μm or more are 4%.
It had a particle size distribution containing 3.8% by volume. At this time, the ratio of the amount of the finally obtained medium powder to the total amount of the charged powder raw materials (that is, the classification yield) was 78% by mass.
Met.

With respect to 100 parts of the middle powder Ad-2,
0.5 part of hydrophobic silica fine powder (BET 300 m ² / g) was externally added by a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain a toner for evaluation.

In the toner (particles), a particle having a circularity of 3 μm or more has a circularity of 0.900 or more in a number-based cumulative value of 90.9% and a particle having a circularity of 0.950 or more in a number. The content was 57.6% as a reference cumulative value, and the cut ratio Z at this time was 40.6%. The toner (this) satisfies the requirements of the present invention in relation to the circularity and the weight average particle diameter (see FIG. 12).

<Example 11> 100 parts of the intermediate powder Aa-2 obtained in Example 1 was added to the hydrophobic silica fine powder (B
^2. 1.0 part of ET 300 m ^{2 /} g) and strontium titanate (2.3 μm in average diameter) as inorganic fine powder.
0 parts was externally added with a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain a toner for evaluation (SA).

The toner (sa) is a toner having a circularity of 3 μm or more, a particle having a circularity of 0.900 or more and a particle-based cumulative value of 96.7%, and a particle having a circularity of 0.950 or more. The content was 79.1% as a reference cumulative value, and the cut ratio Z at this time was 52.5%. The toner (sa) satisfied the requirements of the present invention in relation to the circularity and the weight average particle diameter (see FIG. 13).

Example 12 100 parts of the intermediate powder Ab-2 obtained in Example 9 was added to the hydrophobic silica fine powder (B
^2. 0.7 parts of ET 300 m ^{2 /} g) and strontium titanate as inorganic fine powder (average length of 2.3 μm)
0 parts was externally added by a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain a toner for evaluation.

In the toner (g), particles having a circularity of 3 μm or more have a circularity of 0.900 or more and a particle-based cumulative value of 94.0%. The content was 68.9% as a reference cumulative value, and the cut ratio Z at this time was 64.0%. The toner satisfies the requirements of the present invention in the relationship between the circularity and the weight average particle diameter (see FIG. 13).

<Example 13> To 100 parts of the intermediate powder Ad-2 obtained in Example 10, 0.5 parts of hydrophobic silica fine powder (BET 300 m ² / g) and titanic acid as inorganic fine powder were used. Strontium (average length diameter 2.3 μm)
3.0 parts were externally added with a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain a toner for evaluation.

The toner (s) has a particle-based equivalent particle diameter of 3 μm or more, a particle having a circularity of 0.900 or more and a particle-based cumulative value of 92.1%, and a particle having a circularity of 0.950 or more. The content was 62.0% as a reference cumulative value, and the cut ratio Z at this time was 73.3%. The toner (s) satisfies the requirements of the present invention in relation to the circularity and the weight average particle diameter (see FIG. 13).

Comparative Example 3 Powder raw material A was pulverized and classified by an apparatus system shown in FIG. However, the crusher shown in FIG. 10 is used as the impingement airflow crusher, the first classifier (122 in FIG. 8) has the structure shown in FIG. 9, and the second classifier (127 in FIG. 8) is used. Used the one shown in FIG.

In FIG. 9, reference numeral 401 denotes a cylindrical main body casing, 402 denotes a lower casing, and a hopper 403 for discharging coarse powder is connected to a lower portion thereof. A classification chamber 404 is formed inside the main body casing 401. The classification chamber 404 is closed by an annular guide chamber 405 attached to the upper part of the classification chamber 404 and a conical (umbrella-shaped) upper cover 406 having a high center. I have.

A plurality of louvers 407 arranged in the circumferential direction are provided on a partition wall between the classifying 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 classifying chamber. It is swirled into 404 to flow.

The upper part of the guide chamber 405 is formed by 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 below the main body casing 401, and classifying air causing a swirling flow from the outside to the classification chamber 404 is supplied to the classification louver 4.
09 is taken in.

At the bottom of the classifying chamber 404, a conical (umbrella-shaped) classifying plate 410 having a raised central portion is provided.
A coarse powder discharge port 411 is formed around the outside. 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 fine powder collecting means such as a cyclone and a dust collector, and applies a suction force to the classification chamber 404 by the suction fan, and flows into the classification chamber 404 from between the louvers 409. The swirling flow required for classification is caused by the suction air.

In this comparative example, an air flow type classifier having the above structure was used as the first classifying means, but the air containing the crushed material for toner production was supplied from the supply cylinder 408 into the guide chamber 405. Then, the air containing the crushed material passes between the guide chamber 405 and each louver 407 and passes through the classification chamber 404.
While flowing, it flows in while being dispersed at a uniform concentration.

The crushed material that has flowed into the classifying chamber 404 while swirling is swirled by the suction air flow generated from the suction fan connected to the fine powder discharge chute 412 and flowing from between the classifying louvers 409 below the classifying chamber. The fine powder that is centrifuged into coarse powder and fine powder by the centrifugal force acting on each particle, and is circulated around the outer periphery in the classification chamber 404 is discharged from the coarse powder discharge port 411 and discharged from the lower hopper 403. . Fine powder moving to the center along the upper inclined surface of the classification plate 410 is discharged by the fine powder discharge chute 412.

The table material-type first fixed-quantity feeder 121 supplies the pulverized raw material at a rate of 13.0 kg / h through an injection feeder 135 to a gas flow classifier shown in FIG. The particles were classified by centrifugation using the centrifugal force acting on. The classified coarse powder is supplied through a coarse powder discharge hopper 403 from a supply port 165 of the material to be pulverized shown in FIG.
a, after being pulverized using compressed air of 6.0 m ³ / min, while being mixed with the toner pulverization raw material supplied at the raw material introduction section, the pulverized water is again circulated through the airflow classifier to perform closed circuit pulverization. went. On the other hand, the classified fine powder is entrained by the suction air from the exhaust fan, and
27 and collected by cyclone 131.

In this case, the finely pulverized product Ae-1 has a weight average diameter of 6.6 μm, 65.5% by number of particles having a particle diameter of 4.0 μm or less, and a particle diameter of 10.1 μm or more having a particle diameter of 10.1 μm or more. It had a particle size distribution containing 10.7% by volume of particles. The obtained finely pulverized product Ae-1 was supplied to the vibration feeder 125, the nozzles 148 and
In order to classify the coarse powder, the medium powder Ae-2, and the fine powder through the use of the Coanda effect at a rate of 15.0 kg / h through an air stream 9, the sample was introduced into an airflow classifier shown in FIG. . At the time of introduction, a suction force derived from the reduced pressure in the system due to the reduced pressure of the collection cyclones 129, 130 and 131 communicating with the outlets 158, 159 and 160 was used. Among the classified materials, the coarse powder was collected by the collection cyclone 129, and then introduced into the above-described collision type air current pulverizer 128 at a rate of 0.8 kg / h, and again introduced into the pulverization step.

The intermediate powder Ae- classified in the above classification step
2 (classified product) has a weight average diameter of 6.8 μm, 21.3% by number of particles having a particle diameter of 4.0 μm or less, and a particle diameter of 11.3.
It has a particle size distribution containing 2.2% by volume of particles of 0.1 μm or more, and at this time, the ratio of the amount of the finally obtained medium powder to the total amount of the charged powder raw materials (ie, Classification yield) was 70% by mass.

With respect to 100 parts of the medium powder Ae-2,
Hydrophobic silica fine powder (BET30m ^Two/ G) 1.0 part
Externally added toner with Henschel mixer for evaluation
(T).

In the toner (ta), among particles having an equivalent circle diameter of 3 μm or more, the particles having a circularity of 0.900 or more are 92.1% in terms of the cumulative value based on the number, and the particles having a circularity of 0.950 or more are counted as a number. The content was 59.9% as a reference cumulative value, and the cut ratio Z at this time was 19.6%. The toner (ta) did not satisfy the requirements of the present invention in the relationship between the circularity and the weight average particle diameter (see FIG. 12).

Comparative Example 4 Powder material A was ground in the same manner as in Comparative Example 3 except that the pulverizing pressure in the pulverizing step was changed to 0.4 MPa. The obtained finely pulverized product Af-1 was obtained.
Has a weight average diameter of 10.5 μm and a particle diameter of 4.0 μm
The following particles contained 54.4% by number, and particles having a particle size of 10.1 μm or more contained 55.1% by volume.

Next, the obtained finely pulverized product Af-1 was classified in the same manner as in Comparative Example 3, and the classified medium powder Af-2 (classified product) had a weight average diameter of 10.6 μm. , Particle size 4.0
2.5% by number of particles of μm or less, and particle size of 10.1 μm
It had a particle size distribution containing 52.5% by volume of the above particles. At this time, with respect to the total amount of
Ratio of quantity of medium powder finally obtained (that is, classification yield)
Was 76% by mass. To 100 parts of the medium powder Af-2, a hydrophobic silica fine powder (BET 300 m ² /
g) 0.5 part was externally added using a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain an evaluation toner (C).

In the toner (c), particles having a circularity of 3 μm or more, particles having a circularity of 0.900 or more have a cumulative value of 88.6% based on the number, and particles having a circularity of 0.950 or more have a number of particles. The content was 51.3% as a reference cumulative value, and the cut ratio Z at this time was 34.5%. The toner (c) did not satisfy the requirements of the present invention in the relationship between the circularity and the weight average particle diameter (see FIG. 12).

<Comparative Example 5> Medium powder A obtained in Comparative Example 3
e-2 100 parts with hydrophobic silica fine powder (BE
T300 m ^{2 /} g) 1.0 part and strontium titanate (average length diameter 2.3 μm) 3.0 as inorganic fine powder
Was added externally using a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain a toner for evaluation.

In the toner (1), among particles having an equivalent circle diameter of 3 μm or more, the number of particles having a circularity of 0.900 or more was 93.3% as a cumulative value based on the number, and the number of particles having a circularity of 0.950 or more was counted. The content was 61.6% as a reference cumulative value, and the cut rate Z at this time was 66.7%. The relationship between the circularity and the weight average particle size did not satisfy the requirements of the present invention (see FIG. 13).

<Comparative Example 6> Medium powder A obtained in Comparative Example 4
f-2 100 parts, hydrophobic silica fine powder (BE
T300 m ^{2 /} g) 0.5 part and strontium titanate (in average length of 2.3 μm) 3.0 as inorganic fine powder
Was added externally using a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain a toner for evaluation (te).

In the toner (T), among particles having an equivalent circle diameter of 3 μm or more, particles having a circularity of 0.900 or more are counted as 84.4% in terms of the cumulative value based on the number, and particles having a circularity of 0.950 or more are counted as a number. The content was 55.8% as a reference cumulative value, and the cut ratio Z at this time was 79.4%. The relationship between the circularity and the weight average particle size did not satisfy the requirements of the present invention (see FIG. 13).

[Evaluation] The toners (A) to (T) of the above Examples and Comparative Examples were measured using a Canon laser beam printer LBP-A309GII (using an OPC photosensitive drum).
The test was performed using a remodeled machine that was remodeled from 6 sheets / min to 24 sheets / min.

In the remodeling machine, a charging roller to which a DC bias and an AC bias are applied is applied to the OPC photosensitive drum at a linear pressure of 22.6 × 10 ⁻³ MPa (linear pressure before remodeling of 12.6 × 10 ⁻³ MPa).
The surface of the OPC photosensitive member was charged to a negative potential while being pressed at 7.4 × 10 ⁻³ MPa). As a developing sleeve of a developing device, a developing sleeve having a phenol resin layer in which graphite and carbon black are dispersed on the surface of a cylindrical aluminum enclosing a magnet is used, and has a negative triboelectric charge using an elastic coating blade. A one-component magnetic developer was applied on the developing sleeve. A digital latent image (electrostatic image) formed on the OPC photosensitive drum is developed by a reversal phenomenon method to form a toner image, and the toner image is transferred to a transfer paper (normally) using a transfer roller to which a DC bias is applied. Paper). Transfer roller has a linear pressure of 20.2 ×
The OPC photosensitive drum was set so as to press it at 10 ⁻³ MPa. Next, the toner image on the transfer paper was fixed by a heat and pressure fixing unit having a heating roller and a pressure roller.

Under the above set conditions, under normal temperature and normal humidity environment (20
℃, 60% RH) and low temperature and low humidity environment (15 ℃, 10%
RH) in print mode of 24 sheets / min.
An image output test of 000 sheets was performed. At this time, the following items (1) to (3) were evaluated. These results are summarized in Table 3.

(1) Image Density and Fog The image density was evaluated by maintaining the image density at the end of printing out 8,000 sheets of plain paper for ordinary copying machines. The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth) with respect to the printout image of the white background portion where the original density was 0.00. The fog is measured in advance using a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) to determine the whiteness (%) of the transfer paper before printing, and the whiteness (%) of the transfer paper after printing the solid white image. The value at one point where the difference between the two was maximum was measured, and the maximum value was recorded throughout the endurance. The environment was a low-temperature and low-humidity environment (15 ° C., 10% RH), and the print mode was 2 sheets / 20 seconds.

(2) Transfer Rate The transfer rate of the toner image from the OPC photosensitive drum to the transfer paper at the beginning and end of the endurance of 8,000 sheets was determined by the following method in a normal temperature and normal humidity environment.

The transfer rate of the toner image from the OPC photosensitive drum to the transfer paper was determined by taking a toner image (image density of about 1.3) formed on the OPC photosensitive drum with a transparent adhesive tape and measuring the image density with a Macbeth image. Densitometer or color reflection densitometer (eg, Color reflection densit)
meter X-RITE 404A manufa
cut by X-Rite Co. ). Next, a toner image is formed on the OPC photosensitive drum again,
The toner image was transferred to transfer paper, and a toner image on the transfer paper corresponding to the collected toner image on the OPC photosensitive drum was collected with a transparent adhesive tape, and the image density was measured in the same manner. The transfer rate was calculated from the following equation.

[0250]

(Equation 3)

(3) Fixing property Under normal temperature and normal humidity environment, 5
100 images of 9 mm square solid black (3 rows, 3 rows)
The fixed image is rubbed with a soft thin paper under a load of 4.9 × 10 ⁻³ MPa, and the worst rate of reduction (%) in image density before and after rubbing is performed. The value was evaluated.

[0252]

[Table 1]

[0253]

[Table 2]

[0254]

[Table 3]

[0255]

As described above, according to the present invention,
Good low-temperature fixability, high transfer efficiency toner can be obtained with high yield, and high quality images can be obtained.

[Brief description of the drawings]

FIG. 1 is a flowchart illustrating a method for manufacturing a toner according to the present invention.

FIG. 2 is a schematic diagram showing a specific example of an apparatus system for performing the toner manufacturing method of the present invention.

FIG. 3 is a schematic sectional view of an example of a mechanical pulverizer used in a pulverizing step of the toner of the present invention.

FIG. 4 is a schematic cross-sectional view taken along a line DD ′ in FIG. 3;

FIG. 5 is a perspective view of the rotor shown in FIG. 3;

FIG. 6 is a schematic cross-sectional view of a multi-split airflow classifier used in the toner classifying step of the present invention.

FIG. 7 is a flowchart for explaining a conventional manufacturing method.

FIG. 8 is a system diagram showing a conventional manufacturing method.

FIG. 9 is a schematic cross-sectional view of an example of a classifier used for a conventional first classifier.

FIG. 10 is a schematic sectional view of a conventional collision-type airflow pulverizer.

FIG. 11 is a schematic sectional view of a multi-split airflow classifier used for a conventional second classifier.

FIG. 12 is a graph showing a relationship between a weight average particle diameter X and a number-based cumulative value Y of particles having a circularity of 0.950 or more in Examples and Comparative Examples of the present invention.

FIG. 13 is a graph showing the relationship between the weight average particle diameter X and the number-based cumulative value Y of particles having a circularity of 0.950 or more in Examples and Comparative Examples of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Multi-divider classifier 2 2nd fixed-quantity feeder 3 Vibration feeder 4,5,6 Collection cyclone 11,12,13 Discharge port 11a, 12a, 13a Discharge conduit 14.15 Inlet pipe 16 Material supply nozzle 17,18 Classification edge DESCRIPTION OF SYMBOLS 19 Inlet edge 20 1st gas introduction adjustment means 21 2nd gas introduction adjustment 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 nozzle 42 Raw material powder introduction nozzle 65 Injection feeder 121 First quantitative feeder 122 First classifier 123 Collection cyclone 124 Second quantitative feeder 125 Vibration feeder 127 Multi-divider classifier (second classifier) 128 Air flow Type crusher 129,130,131 Collection cyclone 13 Injection feeders 141, 142 Side walls 143, 144 Classification edge block 145 Coanda block 146, 147 Classification edge 148, 149 Raw material supply pipe 150 Classification chamber upper wall 151 Inlet edge 153, 153 Inlet pipe 154, 155 Gas introduction control means 156, 157 Static pressure gauge 158, 159, 160 Discharge port 161 High-pressure gas supply nozzle 162 Acceleration tube 163 Acceleration tube outlet 164 Collision member 165 Raw material supply port 166 Collision surface 167 Crushed material discharge port 212 Spiral chamber 219 Pipe 220 Distributor 222 Bag filter 224 Suction filter 229 Collection cyclone 301 Mechanical pulverizer 302 Powder discharge port 310 Stator 311 Powder input port 312 Rotary shaft 313 Casing 314 Rotor 315 First fixed amount feeder 3 16 Jacket 317 Cooling water supply port 318 Cooling water discharge port 320 Rear chamber 321 Cold air generating means 331 Third quantitative feeder 401 Main body casing 402 Lower casing 403 Coarse powder discharge hopper 404 Classification chamber 405 Guide chamber 406 Upper cover 407 Louver 408 Supply Tube 409 Classification louver 410 Classification plate 411 Coarse powder discharge port 412 Fine powder discharge chute

Continuing on the front page (72) Inventor Tsutomu Onuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Katsuhisa 3-3-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Kaori Hiratsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Hirohide Tanigawa 3-30-2 Shimomaruko 3-chome, Ota-ku, Tokyo F-term inside Canon Inc. 2H005 AA01 AA06 AB04 CA04 CA13 CA14 EA03 EA05 EA06 EA07 EA10

Claims (9)

[Claims] 1. A toner having at least a binder resin, a colorant and a wax, wherein the wax is added in an amount of 0.2 parts by mass to 100 parts by mass of the binder resin component.
The toner has a maximum endothermic peak temperature of a DSC curve measured by a differential scanning calorimeter of 60 to 100 ° C, a weight average particle diameter X of the toner is 5 to 12 µm, and For particles having a circle equivalent diameter of 3 μm or more of the toner,
The particles having a circularity a of 0.900 or more determined by the following equation (1) have a cumulative value of 90% or more based on the number, and the circularity a = L ₀ / L (1) [where L ₀ is the particle L indicates the perimeter of a circle having the same projected area as the image, and L indicates the perimeter of the particle image. ] And a toner satisfying the following a) or b). a) The relationship between the cut rate Z and the toner weight average particle diameter X satisfies the following expression (2), and the cut rate Z ≦ 5.3 × X (2) [where the cut rate Z is the particle concentration of all the measured particles. Is A (number / μl), and the concentration of measured particles having a circle equivalent diameter of 3 μm or more is B
(Number / μl), it is expressed by the following equation (3). Z = (1−B / A) × 100 (3)
And the number-based cumulative value Y of the particles having a circularity of 0.950 or more.
And the relationship between the toner weight average particle diameter X satisfies the following expression (4). Number-based cumulative value of particles having a circularity of 0.950 or more Y ≧ exp 5.51 × X ^{−0.6 45} (4) [However, toner weight average particle diameter X: 5.0 to 12.0 μm]
m] or b) the relationship between the cut rate Z and the toner weight average diameter X satisfies the following formula (5), the cut rate Z> 5.3 × X (5), and the particles having a circularity of 0.950 or more Number-based cumulative value Y
And the relationship between the toner weight average particle diameter X satisfies the following expression (6). Number basis cumulative value of circularity of 0.950 or more particles ^{Y ≧ exp5.37 × X -0.5 45 (} 6) [ where toner weight-average particle size X: 5.0~12.0μ
m] 2. The wax has a maximum endothermic peak temperature of 60 to 10 in a DSC curve measured by a differential scanning calorimeter.
The toner according to claim 1, wherein the temperature is 0 ° C. 3. The molecular weight distribution of the THF-soluble component of the toner, as measured by GPC, is from 3,000 to 3,000.
The toner according to claim 1, wherein the toner has at least one peak in a region of 50,000 and has at least one peak or shoulder in a region of molecular weight of 50,000 to 10,000,000. 4. The toner is produced through a melt-kneading step, a fine pulverizing step and a classifying step, and is obtained by melt-kneading a mixture containing at least a binder resin, a colorant and a wax. After cooling the kneaded material, the cooled material is coarsely pulverized by a pulverizing means, and the obtained powdery raw material composed of the coarsely pulverized material is introduced into a first constant-volume feeder, and at least from a rotating body attached to a central rotating shaft. And a stator arranged around the rotor while maintaining a constant distance from the rotor surface, and the annular space formed by maintaining the distance is airtight. A predetermined amount of powdered raw material is introduced from the first fixed-quantity feeder through a powder inlet of the mechanical pulverizer into the mechanical pulverizer configured as described above; By rotating the powder at high speed The finely pulverized material is discharged from a powder discharge port of a mechanical pulverizer and introduced into a second quantitative feeder, and a predetermined amount of the finely pulverized material is discharged from the second quantitative feeder. Introduced into a multi-divided airflow classifier that classifies powder using the crossed airflow and Coanda effect, and the pulverized material is converted into at least fine powder, medium powder, and coarse powder in the multi-divided airflow classifier. The classified coarse powder is mixed with a powder material, introduced into the mechanical pulverizer, pulverized, and produced from the classified medium powder. The toner according to any one of the above. 5. The multi-split airflow classifier includes a raw material supply nozzle, a raw material powder introduction nozzle, and a high-pressure air supply nozzle on an upper surface of the multi-split airflow classifier. Classification edge block with edge,
The toner according to claim 4, wherein the toner is a multi-split airflow classifier whose position can be changed so that the shape of the classification area can be changed. 6. The wax having a penetration at 25 ° C. of 1
The toner according to any one of claims 1 to 5, wherein the thickness is less than 0 mm. 7. The wax has a number average molecular weight measured by GPC of 100 to 1000 in terms of polyethylene.
The toner according to any one of claims 1 to 6, wherein 8. In a molecular weight distribution of a THF-soluble component of the toner measured by GPC, a molecular weight of 3,000 to
8. The compound according to claim 3, wherein the compound has at least one peak in a region of 30,000 and has at least one peak or shoulder in a region of a molecular weight of 100,000 to 5,000,000. Toner. 9. The toner according to claim 1, wherein said wax is selected from paraffin wax, Fischer-Tropsch wax, and polyethylene wax.