JP2002107991A - Toner, method of forming image and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which is able to maintain good fixability and free from the generation of image blurring or mutual fusion with a drum. SOLUTION: The toner contains at least a binder resin, a magnetic body and wax. In the toner, the particles having particle sizes of >=3 μm are characterized in that the particles having circularities (a) or >=0.900 are contained in an amount of >=90% expressed in terms of the accumulation value based on the number of particles, the particles having circularities (a) of >=0.950 are contained in an amount of >=67% expressed in terms of the accumulation value based on the number of particles, the particles having circularities (a) of >=0.955 are contained in an amount of >=8% expressed in terms of the accumulation value based on the number of particles, and the existence ratio of the particles having circularities (a) of >=0.955 to the accumulation value based on the number of the particles having circularities (a) of >=0.950 is >=12%. The toner is characterized in that endothermic peaks are found in the temperature regions of 50 to 120 deg.C and 120 to 180 deg.C on the endothermic curve obtained by DSC measurement of the toner using a differential scanning calorimeter when temperature is raised.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic technology, and relates to an electrostatic image developing toner (hereinafter referred to as "toner") for developing an electrostatic latent image, and an image forming method using the toner. And a process cartridge.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
A large number of devices are known as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, but generally a photoconductive substance is used. An electric latent image is formed on the photoreceptor by various means, and then the latent image is developed using toner. If necessary, a toner image is transferred to a transfer material (recording material) such as paper, and then heated. The toner is fixed by heat, pressure, heat or pressure, or a solvent vapor to obtain a copy, and the remaining toner not transferred onto the photoreceptor is cleaned by various devices.
The above steps are repeated.

[0003] In recent years, in such devices, how to reduce power consumption has become an important technical problem from the viewpoint of energy saving. The most effective means for reducing the power consumption depends on how to reduce the power consumption of the fixing device.

[0004] As means for achieving low-temperature fixability,
JP-A-5-197192 proposes a toner having a wax having an endothermic peak in a temperature range of 70 to 130 ° C. in an endothermic curve at the time of temperature rise in DSC measurement measured by a differential scanning calorimeter. There are problems to be improved from the viewpoint of the anti-offset property and the prevention of contamination of the pressure roller described below.

On the other hand, as an apparatus for fixing a visible image of toner on a recording material, a heating roller maintained at a predetermined temperature,
A heat roller fixing method in which a recording material holding an unfixed toner visible image is heated while being nipped and conveyed by a pressure roller having an elastic layer and pressed against the heat roller is often used. Alternatively, a belt fixing system described in U.S. Pat. No. 3,578,797 is known.

However, in the above-described conventional heat roller fixing method, there are (1) a time period during which the image forming operation is prohibited until the heat roller reaches a predetermined temperature, that is, a so-called wait time; It is necessary to maintain the heating roller at an optimum temperature in order to prevent fixing defects due to fluctuations in the temperature of the heating roller due to other external factors and transfer of the developer to the heating roller, so-called offset phenomenon. Therefore, the heat capacity of the heating roller or the heating element must be increased, which requires a large amount of electric power. (3) Since the temperature of the roller is low, when the recording material is discharged through the heating roller, Since the recording material and the developer on the recording material are slowly cooled, the adhesiveness of the developer becomes high,
In combination with the curvature of the roller, a paper jam may occur due to offset or entanglement of the recording material; (4) a configuration in which the high-temperature heating roller directly touches the hand,
There is a problem with safety or a need for a protective member;

Also, in the belt fixing method described in US Pat. No. 3,578,797, the above-mentioned problems (1) and (2) of the heat roller fixing have not been fundamentally solved.

[0008] JP-A-63-313182 by the present applicant
In Japanese Patent Laid-Open Publication No. 2 (1995) -207, an image forming method of heating a toner-visible image through a heat-resistant sheet that moves by a low-heat-capacity heat-generating body heated in a pulsed manner and fixing the image on a recording material has a short wait time and a low wait time. 2. Description of the Related Art An image forming apparatus with low power consumption has been proposed.

In the heating method using a heating roller or a film, the toner image surface of a sheet to be fixed is passed through the surface of a heat roller or a film formed of a material having a releasable property with respect to the toner, while the surface is in contact therewith. The fixing is performed by the following. In this method, since the surface of the heat roller or the film comes into contact with the toner image of the sheet to be fixed, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. It is very effective in electrophotographic copying machines.

However, in the above method, since the surface of the heat roller or the film contacts the toner image in a molten state,
A part of the toner image adheres and transfers to the fixing roller or the film surface, and re-transfers to the next sheet to be fixed, causing a so-called offset phenomenon, which may stain the sheet to be fixed. Preventing the toner from adhering to the heat fixing roller or the film surface is one of the essential conditions of the heat fixing method.

In recent years, the use of recycled paper has been increasing year by year from the viewpoint of environmental problems and resource protection. Among these recycled papers, a large amount of additives such as calcium carbonate is used for the purpose of improving the whiteness of the paper. There is a thing contained in. When these papers are used, there is a problem that the additive and toner separated from the paper accumulate on the pressing member of the image forming method and appear as image stains (hereinafter referred to as "pressure roller stains"). The problem of the image contamination is becoming more serious due to the downsizing and power saving of the fixing device for achieving the downsizing of the printer device and the speeding up of the printer device.

A laser beam printer is generally used in an office at normal temperature and normal humidity, but may be used in a high temperature and high humidity environment in areas such as Southeast Asia and India. In such an environment, a phenomenon (hereinafter, referred to as "image deletion") in which a latent image on the surface of the photoreceptor is significantly damaged by a low electric resistance substance formed by paper dust, ozone, or the like generated during printing is likely to occur.

As means for solving such a problem, JP-A-62-160458 discloses a photoreceptor having a photosensitive layer containing two kinds of polycarbonate resins having different molecular weights. Further, as a means for preventing image deletion, Japanese Patent Application Laid-Open No. 60-32060 discloses two types of BEs.
A toner containing an inorganic fine powder having T is disclosed. When an image is formed using the photoreceptor and toner according to the invention disclosed in the above publication, the image deletion is improved, but the toner or the like is pressed on the photoreceptor surface by a charging member or the like and adheres to the photoreceptor. (Hereinafter referred to as “drum fusion”).

There is an urgent need to solve the above problems.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner, an image forming method, and a process cartridge which achieve good fixing performance, have excellent offset resistance, and do not cause contamination of a pressure roller. Is to do.

It is a further object of the present invention to provide a toner, an image forming method and a process cartridge which do not cause image deletion in a high-temperature and high-humidity environment and do not cause drum fusing in all environments. It is in.

[0017]

The present invention relates to a toner containing at least a binder resin, a magnetic substance and a wax, wherein a particle having a circularity a of 3 μm or more is determined by the following formula (A). Is 90% or more in terms of the number-based cumulative value of particles having a number of 0.900 or more, and the circularity a
Are present in a number-based cumulative value of 67% or more, and particles having a circularity a of 0.995 or more are present in a number-based cumulative value of 8% or more, and the circularity a Is 0.995 or more, and the circularity a is 0.950.
12% or more of the number-based cumulative value of the above particles is present,

[0018]

[Outside 10]

(In the formula, 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.) At the time of temperature rise in the DSC measurement by the differential scanning calorimeter of the toner. In the endothermic curve, a temperature range of 50 ° C. to 120 ° C. and 1
The present invention relates to a toner having an endothermic peak in a temperature range of more than 20 ° C. to 180 ° C.

Further, according to the present invention, an electrostatic image carrier for carrying an electrostatic image is charged, an electrostatic image is formed on the charged electrostatic image carrier, and the electrostatic charge is formed by a toner of a developing means. Developing the image to form a toner image, transferring the toner image on the electrostatic image carrier to a transfer material with or without an intermediate transfer member, and using a heat-resistant film and a heating element via the heat-resistant film The heat conductivity is 0.2
By using a heat-fixing device that sandwiches and conveys the transfer material and applies thermal energy to the transfer material between a pressing member having a heat-resistant elastic layer of 0 W / m · k or less on a metal core, In an image forming method for fixing a toner image on a transfer material to the transfer material, the toner contains at least a binder resin, a magnetic substance, and a wax, and in a particle of 3 μm or more of the toner, the following formula (A) is used. Particles whose required circularity a is 0.900 or more have a cumulative number-based value of 90% or more, and particles whose circularity a is 0.950 or more exist in a number-based cumulative value of 67% or more, In addition, the circularity a is 0.
995 or more particles exist in a number-based cumulative value of 8% or more, and the abundance of particles having a circularity a of 0.995 or more is reduced to the number-based cumulative value of particles having a circularity a of 0.950 or more. At 12% or more,

[0021]

[Outside 11]

(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.) At the time of DSC measurement of the toner by a differential scanning calorimeter, The image forming method has an endothermic peak in a temperature range of 50 ° C. to 120 ° C. and a temperature range of more than 120 ° C. to 180 ° C. in the endothermic curve.

Further, the present invention relates to a process cartridge detachably mounted on an image forming apparatus main body, wherein the process cartridge includes an electrostatic image carrier for carrying an electrostatic image and an electrostatic image carrier. Developing means for holding the toner for developing the electrostatic charge image carried thereon to form a toner image, wherein the toner is a toner containing at least a binder resin, a magnetic substance, and a wax; In the toner particles having a particle size of 3 μm or more, the circularity a obtained by the following formula (A) is 90% or more in terms of the number-based cumulative value of the particles having a circularity a of 0.900 or more, and the circularity a
Are present in a number-based cumulative value of 67% or more, and particles having a circularity a of 0.995 or more are present in a number-based cumulative value of 8% or more, and the circularity a Is 0.995 or more, and the circularity a is 0.950.
12% or more of the number-based cumulative value of the above particles is present,

[0024]

[Outside 12]

(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.) At the time of DSC measurement of the toner by a differential scanning calorimeter, A process cartridge having endothermic peaks in a temperature region of 50 ° C. to 120 ° C. and a temperature region of more than 120 ° C. to 180 ° C. in the endothermic curve.

According to the present invention, the toner particles have a certain degree of circularity within a certain range, and in an endothermic curve at the time of temperature rise in DSC measurement, at least one endothermic peak is present in each of a low temperature region and a high temperature region. The toner has a specific thermal characteristic that the toner has good low-temperature fixability and anti-offset property, and can further prevent contamination of the pressure roller.

Conventionally, in the case of a toner having a general circularity and at least one peak in a high temperature region or a low temperature region, it has been possible to satisfy either the low-temperature fixing property or the offset resistance. However, it was difficult to achieve both, and the level of prevention of pressure roller contamination was insufficient.

With respect to the contamination of the pressure roller, when there are many magnetic particles or free magnetic substances existing on the surface of the magnetic toner particles,
It is presumed that magnetic particles and the like are likely to selectively adhere to the surface of the pressure roller, and using this as a nucleus, contamination of the pressure roller becomes worse. In order to have a certain degree of circularity, for example, in the case of manufacturing by a pulverization method, the toner is pulverized by a mechanical impact force, but the resin on the toner particle surface is crushed by a certain mechanical impact force. It is presumed that slight melting of the wax occurs instantaneously, and an appropriate circularity is obtained. It is considered that the release of the magnetic substance and the exposure of the magnetic substance to the surface of the toner particles are suppressed by this.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a toner according to the present invention will be described.

The toner suitably used in the present invention contains at least a binder resin, a magnetic substance, and a wax, and has a circularity a of 0.900 in the particles of 3 μm or more obtained by the following formula (A). The above particles are present in a cumulative value of 90% or more based on the number, and the circularity a is 0.950.
The above particles are present in a number-based cumulative value of 67% or more, and the particles having a circularity a of 0.995 or more are present in a number-based cumulative value of 8% or more, and the circularity a is 0.995 or more. Is present in a proportion occupying 12% or more with respect to the cumulative value based on the number of particles having a circularity a of 0.950 or more in the circularity a, and the toner was measured at the time of temperature rise by DSC measurement with a differential scanning calorimeter. The endothermic curve is characterized by having endothermic peaks in a temperature range of 50 ° C. to 120 ° C. and in a temperature range of more than 120 ° C. to 180 ° C., respectively.

[0031]

[Outside 13]

(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.) The present inventors have determined the shape of the toner and the thermal characteristics of the toner. It has been found that the low-temperature fixing property, the offset resistance, the pressure roller stain, and the drum fusing phenomenon are closely related.

That is, when the toner having the shape of the present invention is produced by, for example, mechanical impact, the resin on the particle surface is melted by the grinding action, and the resin on the particle surface changes the magnetic material on the toner particle surface. cover. As a result, the toner having a circularity according to the present invention has a shape close to a sphere and suppresses the exposure of the magnetic material as compared with a toner manufactured by a normal pulverization method.

When the magnetic material is exposed to a large amount, the phenomenon that the toner transferred from the fixing film to the pressure roller easily adheres to the surface of the pressure roller or the phenomenon that the toner is easily scratched on the photosensitive drum becomes apparent. Become

Therefore, when the toner of the present invention is used,
By suppressing the particle surface exposure of the magnetic material, it is possible to reduce the occurrence of contamination of the pressure roller and the phenomenon of drum fusion.

Further, the toner of the present invention has one or more endothermic peaks in each of a low temperature region and a high temperature region in an endothermic curve at the time of temperature rise in DSC measurement, thereby ensuring low-temperature fixing and offset resistance. It is possible to do.

When a toner having a specific circularity is manufactured, the weight average particle size is 5 to 10 μm, the particles having a particle size of 4 μm or less are 40% by number (15% by volume) or less, and the particle size is 10.1 μm or more. It is preferable that the toner is 25% by volume (5% by number) or less.

When a toner having a weight average diameter exceeding 10 μm is obtained, the load in the pulverizer tends to be reduced as much as possible, making it difficult to obtain a desired circularity distribution of the toner particles. It is difficult to successfully prevent wearing.

When a toner having a weight average diameter of less than 5 μm is obtained, the load in the pulverizer is increased in a direction that is not preferable in production, but the generation of fine powder or ultrafine powder is increased, and the drum is fused or fogged or cleaned. The occurrence of defects becomes apparent.

25% by volume of particles having a particle size of 10.1 μm or more
In the case of a toner exceeding (5% by number), the same adverse effects as in the case of obtaining a toner having a weight average diameter exceeding 10 μm occur.

40% by number of particles having a particle size of 4.0 μm or less
In the case of a toner exceeding (15% by volume), the same adverse effects as in the case of obtaining a toner having a weight average diameter of less than 5 μm occur.

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 device, 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 measuring method, a surfactant (preferably an alkylbenzene sulfonate) is used as a dispersant in 100 to 150 ml of the electrolytic aqueous solution.
Is added, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample was suspended was treated with an ultrasonic
The dispersion treatment is performed for one minute, and the measurement is performed using a 100 μm aperture with the Multisizer II of the Coulter Counter. 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.

If the number of particles having a circularity a of 0.900 or more is less than 90% in terms of the number-based cumulative value, contamination of the pressure roller and deterioration of drum fusion are unfavorably observed. Even when the number of particles having a circularity a of 0.950 or more is less than 67% in terms of the number-based cumulative value, contamination of the pressure roller and deterioration of the drum fusion are unfavorably observed. Circularity a
Of particles having a value of 0.995 or more is 8 in terms of the number-based cumulative value.
%, It is not preferable because contamination of the pressure roller and deterioration of drum fusion are observed.

Also, when the presence of particles having a circularity a of 0.995 or more is less than 12% with respect to the particles having a circularity a of 0.950 or more, the contamination of the pressure roller and the fusion of the drum can be prevented. Occurrence manifests.

As one measure of such variation of the particles having each circularity, the circularity standard deviation SD can be used. In the present invention, there is no problem if the circularity standard deviation SD is 0.034 to 0.043.

The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of a particle. In the present invention, the average circularity is measured using a flow particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics. Is performed, the circularity of the measured particles is obtained by the following equation (A), and the average circularity obtained by dividing the sum of the circularities of all the particles measured by the following equation (B) by the total number of particles is further obtained. Define.

[0049]

[Outside 14]

(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).

[0051]

[Outside 15]

[0052]

[Outside 16]

[0053]

[Outside 17]

The circularity used in the present invention is an index of the degree of unevenness of the toner particles. When the toner has a perfect spherical shape, the circularity is 1.00, and the circularity becomes smaller as the surface shape becomes more complicated. In addition, the 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.

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 measurement method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impurities have been removed in a container in advance, and further measurement is performed. 0.1
Add about 0.5 g. The suspension in which the sample is dispersed is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the dispersion concentration is adjusted to 3
Using the above-mentioned flow type particle image measuring apparatus, the particle size is determined to be 6,000 to 10,000 particles / μl, and 0.60 μm to 159.21 μm.
The circularity distribution of particles having a circle equivalent diameter of less than is measured.

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 Laid-Open No. 8-136.
No. 439, which is as follows.

The sample dispersion liquid 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.

Further, the toner of the present invention has an endothermic peak in a temperature range of 50 ° C. to 120 ° C. and a temperature range of more than 120 ° C. to 180 ° C. in an endothermic curve at the time of DSC measurement by a differential scanning calorimeter. It is characterized by the following.

By having two peak endothermic characteristics,
It is possible to provide a good toner that achieves good fixability, has excellent offset resistance, and is free from contamination of the pressure roller.

When the position of the endothermic peak on the low temperature side is lower than 50 ° C., the fluidity of the toner tends to be remarkably reduced,
As a defect on the development surface, adverse effects such as a decrease in image density and generation of fog are likely to occur.
It is difficult to achieve good low-temperature fixability.

When the position of the endothermic peak on the high temperature side is 120 ° C. or less, the offset resistance tends to decrease.
When the temperature is higher than 80 ° C., the low-temperature fixing is adversely affected, which is not preferable.

The more preferable range of the endothermic peak on the lower melting point side is 60 to 110 ° C., and the more preferable range of the endothermic peak on the higher melting point side is 130 to 160 ° C.

The toner having the specific DSC endothermic characteristic has a maximum endothermic peak (melting point) of 50 ° C. to 1 ° C. in an endothermic curve at the time of temperature rise in DSC measurement by a differential scanning calorimeter.
It is preferable to contain wax A having a temperature range of 20 ° C. and wax B having a maximum endothermic peak (melting point) of more than 120 ° C. to 180 ° C.

Hereinafter, the constitution of the toner of the present invention will be described in detail.

The toner of the present invention comprises at least a binder resin,
Contains magnetic material and wax.

Examples of the binder resin of the toner particles used in the present invention include polystyrene; a styrene-substituted homopolymer such as poly-p-chlorostyrene and polyvinyltoluene; and a styrene-p-chlorostyrene copolymer. Styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile Copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene Styrene copolymer such as copolymer Body: polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin , Polyvinyl butyral, terpene resin, cumarone indene resin, petroleum resin and the like can be used. Also,
Crosslinked styrenic resins are also preferred binder resins.

The comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, and the like. Monocarboxylic acid having a double bond such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or the like; maleic acid, butyl maleate, Dicarboxylic acids having a double bond such as methyl maleate, dimethyl maleate, and the like; vinyl esters such as vinyl chloride, vinyl acetate, and vinyl benzoate; ethylene, propylene, butylene, and the like. Vinyl monomers such as vinyl methyl ketone, vinyl hexyl ketone, etc .; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc .; Can be Here, as the cross-linking agent, a compound having two or more polymerizable double bonds is mainly used. Specifically, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, etc .; ethylene glycol diacrylate, ethylene glycol Glycol dimethacrylate, 1,
Carboxylic acid esters having two double bonds such as 3-butanediol dimethacrylate; divinyl compounds such as divinyl aniline, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups; Alternatively, they can be used as a mixture.

The toner used in the present invention contains a magnetic material. The magnetic material used is a metal oxide containing an element such as iron, cobalt, nickel, copper, magnesium, manganese, aluminum or silicon. There are things. Among them, those mainly containing iron oxide such as triiron tetroxide and γ-iron oxide are preferable. Further, from the viewpoint of improving the fluidity of the toner and controlling the chargeability, it is preferable to contain a silicon atom. In particular, when the toner particles have a small diameter, the fluidity of the toner particle base is reduced. Therefore, sufficient fluidity cannot be obtained only by adding the inorganic fine powder of the present invention described above, and good chargeability cannot be obtained. It may be difficult to achieve the above objective. The content of silicon atoms is preferably 0.2 to 2.0% by mass with respect to the magnetic material. If the content is less than 0.2% by mass, sufficient fluidity cannot be obtained, and character sharpness may not be obtained. There are adverse effects such as deterioration and solid black density. If the content is more than 2.0% by mass, especially high temperature
The image density tends to decrease in a high humidity environment. The content of silicon atoms is more preferably 0.3 to 1.7% by mass. In particular, silicon atoms on the surface of
More preferably, it is present in an amount of 5 to 0.5% by mass.

The silicon atom may be added in the form of a water-soluble silicon compound when the magnetic substance is formed. After the formation of the magnetic substance, filtration and drying, it is added in the form of a silicate compound and fixed to the surface by a mix muller or the like. You may. These magnetic particles preferably have a BET specific surface area measured by a nitrogen adsorption method of 2 to 3 times.
0 m ² / g is good, and especially 3 to 28 m ² / g is good. Further, magnetic particles having a Mohs hardness of 5 to 7 are preferred.

The shape of the magnetic particles includes an octahedron, a hexahedron, a sphere, a needle, a scale, and the like, and an octahedron, a hexahedron, a sphere, an irregular shape, or the like having a small anisotropy is preferable.
In particular, it is preferable that the sphericity 磁性 of the magnetic particles be 0.8 or more in order to increase the image density. The average particle size of the magnetic particles is preferably 0.05 to 1.0 μm, more preferably 0.1 to 0.6 μm, and particularly 0.1 to 0.4 μm.
m is preferred.

The content of the magnetic substance in the toner is 30 to 200 parts by mass, preferably 60 to 200 parts by mass, and more preferably 70 to 150 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 30 parts by mass, the transportability is poor, the toner layer on the developer carrier tends to be uneven, and the image tends to be uneven. Further, the image density tends to decrease due to the rise in the tribo of the magnetic toner. Tend. On the other hand, when the content of the magnetic substance exceeds 200 parts by mass, the fixability tends to decrease.

The waxes contained in the toner of the present invention include the following. For example, low molecular weight polyethylene,
Aliphatic hydrocarbon waxes such as low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax;
Or block copolymers thereof; vegetable waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; animal waxes such as beeswax, lanolin, and spermaceti; mineral based waxes such as ozokerite, ceresin, petrolatum. Wax; waxes mainly containing fatty acid esters such as montanic acid ester wax and caster wax; 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,
Saturated alcohols such as carnaubavir alcohol, seryl alcohol, melisyl alcohol, or long-chain alkyl alcohol having a longer-chain alkyl group; polyhydric alcohols such as sorbitol; linoleamide, oleic amide, lauric amide Aliphatic amides; saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N Unsaturated fatty acid amides such as' -dioleyl adipamide, N, N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bis stearamide, N, N'-distearyl isophthalic amide ; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate (commonly referred to as metal soaps); grafted onto aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid Waxes; partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

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.

The thermal properties of the toner used in the present invention are considered to have a high correlation with the melting point of the wax, but it is more preferable that the toner contains two kinds of waxes having different melting points (namely, waxes A and B). That is, the melting point of the low melting point wax A is 50 to 120 ° C, preferably 60 to 110 ° C.
° C, and the melting point of the high melting point wax B is more than 120 to 180.
C, preferably 130-160C. By containing two types of waxes A and B,
The low-temperature fixability and the offset resistance, which are the problems to be solved by the present invention, can be favorably achieved.

When only the low-melting wax A is used, the offset resistance becomes insufficient, and when only the high-melting wax B is used, it is difficult to achieve low-temperature fixability.

The content of the wax in the toner used in the present invention is 0.5 to 100 parts by mass of the binder resin component.
It is preferably from 30 to 30 parts by mass.

If the amount is less than 0.5 part by mass, it is difficult to obtain a toner having a good circularity. If the amount is more than 30 parts by mass, the cohesiveness of the toner increases, and the developability deteriorates remarkably.

In the DSC measurement of the present invention, the exchange of heat between the toner and the wax is measured and the behavior thereof is observed. Therefore, from the measurement principle, it is necessary to measure with a highly accurate internal heating type input compensation type differential scanning calorimeter. is there. For example, DSC-7 manufactured by PerkinElmer can be used. The sample amount used for the measurement is about 10-15 in the case of a toner sample.
mg, about 2-5 m for a wax sample
Use g.

The measuring method is as described in ASTM D3418-82.
Perform according to. The DSC curve used in the present invention has a temperature rate of 10? / Min
A DSC curve measured when the temperature is lowered and raised in a temperature range of 0 to 200 ° is used.

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

Examples of the charge control agent include the following.

As a negative charge controlling agent for making the toner negatively chargeable, 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 control agent that makes the toner positively chargeable include nigrosine, nigrosine derivatives, triphenylmethane compounds, and organic quaternary ammonium salts.

Further, as a preferred embodiment of the toner used in the present invention, it is possible to appropriately add a fluidity improver or an abrasive.

The fluidity improver has a number average diameter of 0.1.
005 to 0.07 μm, for example, fine alumina powder, fine silica powder and the like. Further, these fine powders are preferably those whose surfaces have been subjected to a coupling treatment, an oil treatment, a treatment with a fatty acid or the like.

As the abrasive, those having a number average diameter of 0.12 to 3.0 μm can be preferably used. For example, iron oxide, chromium oxide, calcium titanate, strontium titanate, barium titanate, magnesium titanate,
Cerium oxide, zirconium oxide, aluminum oxide,
There are titanium oxide, zinc oxide, calcium oxide and the like. Strontium titanate, cerium oxide and titanium oxide are preferably used.

The content of the fluidity improver is 0.1 to the toner.
The content is preferably 5 to 2.5% by mass, and the content of the abrasive is preferably 0.35 to 3.5% by mass based on the toner.

Hereinafter, preferred embodiments of the method for producing a toner according to 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 according to the present invention, a mixture containing at least a binder resin, a magnetic substance 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 as a toner raw material composed of a group of particles having a specified particle size. On this occasion,
In the classification step, at least a coarse powder region,
A multi-divided airflow classifier having a medium powder region and a fine powder region is preferably used. For example, when a three-split airflow classifier is used, the powder raw material is classified into at least three types of fine powder, medium powder, and coarse powder. In the classification process using such a classifier, a coarse powder composed of a group of particles having a larger particle size than the preferred particle size and a fine powder composed of a group of particles having a particle size smaller than the preferred particle size are removed, and the medium powder is used as it is as a toner product. Or used after being mixed with an external additive such as hydrophobic colloidal silica.

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 powder raw material composed of the 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. A magnetic resin particle powder containing at least a binder resin, a magnetic substance and a wax is used as a powder raw material that is a toner raw material introduced into the apparatus system. A mixture composed of a magnetic material, 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, first, a predetermined amount of a pulverized raw material serving as a toner powder raw material is 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.

Further, in this apparatus system, the first fixed-quantity feeder 315 sends a mechanical crusher 301 as a crushing 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 When the predetermined amount to be introduced is set to 1, the predetermined amount to be introduced from the second fixed-quantity feeder 2 to the multi-split air classifier 1 is preferably 0.7 to 1.7, more preferably 0.7 to 1.7. 1.5,
More preferably, the ratio is set to 1.0 to 1.2 from the viewpoint of toner productivity and production efficiency.

Normally, the air-flow classifier of the present invention is used by connecting mutual devices with communicating means such as pipes, 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 apparatus 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 / sec. 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 instantaneously divided into three or more types of particles in 0.1 to 0.01 seconds or less. Can be classified. 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. Also, the large particles that are classified at this time are:
It is preferable to re-introduce the mixture into the first fixed supply machine 315, mix it into the powder raw material, and pulverize again with the mechanical pulverizer 301.

The 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. At the same time, the load on the apparatus itself is increased, and at the same time, it is excessively pulverized at the time of pulverization, so that excessive surface modification of the toner due to heat and fusing in the machine are likely to occur, which is not preferable in terms of toner productivity.

In this apparatus system, the particle size of the powder raw material is 95% by 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 with a weight average particle diameter of 10 μm or less (further 8 μm or less) in this apparatus system, the finely pulverized material pulverized by a mechanical pulverizer must be used. Weight average particle size of 4 to 10
μm, 4.00 μm or less is 70% by number or less, and 65% or less.
The number% or less, 10.1 μm or more is preferably 25% by volume or less, more preferably 20% by volume or less. The particle size of the classified medium powder has a weight average particle size of 5 to 10 μm, 4.00 μm.
m is 40% by number or less, 35% by number or less, 1
The volume of 0.1 μm or more is preferably 25% by volume or less, more preferably 20% 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 crusher 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, where the particles are rotated at a high speed. 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, since the powder raw material is pulverized in this manner, a desired pulverization treatment can be easily performed without increasing fine powder and coarse powder.

Further, when the pulverized raw material is pulverized by a mechanical pulverizer, cold air is blown into the mechanical pulverizer together with the powder raw material by the cool air generating means 321. 316, and a cooling water (preferably an antifreeze such as ethylene glycol) is passed therethrough to lower the room temperature T1 (inlet temperature) in the spiral chamber 212 communicating with the powder inlet in the mechanical pulverizer to 0 ° C. Hereinafter, more preferably −5 to −15 ° C., and still more preferably −7 to −12.
C. is preferable from the viewpoint of toner productivity. By controlling the room temperature T1 of the spiral chamber in the pulverizer to 0 ° C. or lower, more preferably −5 to −15 ° C., and still more preferably −7 to −12 ° C., excessive surface modification of the toner due to heat can be suppressed. It is possible to efficiently pulverize the raw material. When the room temperature T1 of the spiral chamber in the crusher exceeds 0 ° C.,
Excessive surface modification of the toner and fusing in the machine due to heat during pulverization are likely to occur, which is not preferable in terms of toner productivity. If the room temperature T1 of the spiral chamber in the crusher is to be operated at a temperature lower than −15 ° C., the above-mentioned cold air generating means 32
The refrigerant (alternative CFC) used in 1 must be changed to CFC.

At present, the 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.

Further, when the pulverized raw material is pulverized by a mechanical pulverizer, the temperature difference ΔT between the room temperature T1 (inlet temperature) of the spiral chamber 212 of the mechanical pulverizer and the room temperature T2 (outlet temperature) of the rear chamber 320.
(T2−T1) is preferably set to 30 to 80 ° C.,
More preferably 35-75 ° C, even more preferably 37-7.
By setting the temperature at 2 ° C., excessive surface modification of the toner due to heat can be suppressed, and the pulverized raw material can be efficiently pulverized. Δ of temperature T1 and temperature T2 of mechanical crusher
If T is less than 30 ° C., short paths 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 excessive surface modification of the toner due to heat and fusing in the machine are likely to occur.

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, excessive surface modification of the toner due to heat can be suppressed, and the pulverized raw material can be efficiently removed. Can be crushed. Also, the room temperature T2 of the rear chamber 320 of the mechanical crusher
Is 5 to 30 ° C., more preferably 10 to 20 ° C. than Tg.
Preferably it is low. By setting the room temperature T2 of the rear chamber 320 of the mechanical pulverizer lower than Tg by 5 to 30 ° C., more preferably 10 to 20 ° C., excessive surface modification of the toner due to heat can be suppressed, and the pulverization can be performed efficiently. Raw materials can be crushed.

The peripheral speed of the tip of the rotating rotor 314 is preferably 80 to 180 m / sec.
It is more preferably 90 to 170 m / sec, and still more preferably 100 to 160 m / sec, from the viewpoint of toner productivity. The peripheral speed of the rotating rotor 314 is set to 80 to 180 m / sec, more preferably 90 to 170 m / sec.
m / sec, more preferably 100 to 160 m / sec
By doing so, 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 / sec, it is not preferable in terms of toner performance because a short path is easily generated without being pulverized. Also, the peripheral speed of the rotor 314 is 180
When the speed is higher than m / sec, 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 likely to be excessively modified by heat and to be fused inside the apparatus.

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. When the distance between the rotor 314 and the stator 310 is smaller than 0.5 mm, the load on the apparatus itself is increased, and at the same time, excessive pulverization at the time of pulverization, excessive surface modification of the toner due to heat, and fusing in the apparatus. This 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 finely divided to increase the electrostatic aggregation between the particles, and 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. The nozzle 16 is provided on the right side of the side wall 22, and the Coanda block 26 is provided so as to draw a long elliptical arc in the extending direction of the lower tangent of the raw material supply nozzle 16.
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 further, on the left side of the classifying chamber 32, there are provided inlet pipes 14 and 15 opening to the classifying chamber 32. It is. In addition, as shown in FIG.
4 and 15 are provided with a first gas introduction adjusting means 20, a second gas introduction adjusting means 21, such as a damper, and a static pressure gauge 28 and a static pressure gauge 29.

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

Further, 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 innermost 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 classification chamber through the raw material supply nozzle 16 at a flow rate of preferably 10 to 350 m / sec, and dispersed.

The particles in the powder introduced into the classifying chamber move in a curved line due to 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 conditions of pulverization and classification, a toner having a sharp particle size distribution having a weight average particle diameter of 10 μm or less (particularly 8 μm or less). Can be generated efficiently.

To prepare the toner of the present invention, a mixture containing at least a binder resin, a magnetic substance and a wax is used as a material. In addition, if necessary, a charge control agent and other additives are used. Used. These materials were thoroughly mixed by a mixer such as a Henschel mixer or a ball mill, and then melted, kneaded and kneaded using a hot kneader such as a roll, kneader and extruder to make the resins compatible with each other. The toner can be obtained by dispersing or dissolving a pigment or dye, cooling and solidifying, and then 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. Is used.

Examples of the mixer include a Henschel mixer (manufactured by Mitsui Mining); a super mixer (manufactured by Kawata); a ribocorn (manufactured by Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron); Pin mixers (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige mixers (manufactured by Matsubo), and kneading machines include KRC kneader (manufactured by Kurimoto Tekkosho);
Co-kneader (manufactured by Buss); TEM extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three-roll mill; And a kneader (manufactured by Inoue Seisakusho); Kneedex (manufactured by Mitsui Mining Co., Ltd.); an MS type pressure kneader, a kneader ruder (manufactured by Moriyama Seisakusho); Further, as a sieving apparatus used for sifting coarse particles and the like, Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona sieve, gyro shifter (manufactured by Tokuju Kosakusho); Vibrasonic System (manufactured by Dalton); Shinto Kogyo Co., Ltd.); Turbo Screener (Turbo Kogyo Co., Ltd.); Micro Shifter (Makino Sangyo Co., Ltd.);

Next, the heat fixing device used in the image forming method of the present invention will be described.

The heat fixing device suitably used for the image forming method and the image forming toner of the present invention comprises a heat-resistant film and a pressing member arranged so as to be in pressure contact with a heating member via the heat-resistant film. A heating and fixing device for applying heat energy to the transfer material by sandwiching and transferring the transfer material between the heat transfer members, wherein the pressing member includes a heat-resistant elastic layer having a heat conductivity of 0.20 W / m · k or less. It is characterized by having on a cored bar.

When the heat conductivity is lower than that of the conventional roller, heat is more easily held on the roller surface than that of the conventional pressure roller, and it has a very advantageous effect on the low-temperature fixability. Further, since the toner adhering to the surface of the roller is easily softened again, the toner can be gradually transferred to the paper, so that the toner is not excessively accumulated on the pressure roller. Incidentally, the temperature of the pressure roller surface during image formation is usually 110 ° C. to 150 ° C.
° C.

The use of the pressure roller of the present invention makes it possible to achieve good fixability and reduce pressure roller contamination even when the fixing speed is 55 mm / sec.
Furthermore, the power consumption of the heating member of the present invention can be suppressed to 0.4 to 0.7 W · h / sheet.

The power consumption was measured as follows.

After the temperature of the heater reaches 200 ° C. in an environment of 23 ° C. and 60% RH, the power consumption until the recording material enters and passes through the nip is measured, and the power consumption per printed image is obtained. Was.

The configuration of the heat fixing device according to the present invention is such that a member to be heated is sandwiched between a heat-resistant film and a pressing member arranged so as to be pressed against a heating body via the heat-resistant film. What has the structure which conveys and gives thermal energy to this heating member is used.

FIG. 14 is a cross-sectional view schematically showing the structure of a tensionless film heating type heat fixing apparatus according to an embodiment of the present invention.

Reference numeral 701 denotes a resin-made horizontally long stay, which serves as an inner surface guide member of a film described later. An endless heat-resistant film 702 is circumscribed to a stay 701 including a heating element 703. A stay 70 including the inner peripheral length of the endless heat-resistant film 702 and the heating element 703
The outer peripheral length of the film 702 is larger than that of the film 702 by, for example, about 3 mm.
The outer circumference loosely circumscribes the stay 701 with the margin.

The film 702 is used to reduce the heat capacity and improve the quick start property.
Has a thickness of about 100 μm or less, and is a single layer of PTFE, PFA, FEP having heat resistance, release property, strength, durability, etc., or polyimide, polyamide, PEEK,
PTFE, PFA, FE on the outer surface of PES, PPS, etc.
A laminated film coated with P or the like can be used.

In this embodiment, the heat-resistant film 7
For 02, the outer peripheral surface of a 50 μm polyimide film was coated with 10 μm PTFE, and the layer thickness was 60 μm.
m was used.

Reference numeral 703 denotes a heating element, which is formed, for example, of Ag / Ag along a substantially central portion of a base made of alumina or the like.
An electric resistance material such as Pd (silver-palladium)
The coating is formed by screen printing or the like to a thickness of 1 μm and a width of 1 to 3 mm, and glass or a fluororesin is coated thereon as a protective layer. A thermistor for the heating element is provided on the opposite side of the heating element from the fixing film, and the temperature of the heating element 703 is controlled by the temperature detected by the thermistor.

The pressure roller 706 is a rotating body that forms a fixing nip with the heating element 703 sandwiching the film 2 and drives the film.
They are connected by a core metal such as aluminum. The pressure roller 706
Are adapted to rotate by transmitting a driving force from a driving motor of a driving device.

The recording material P as a heated member is conveyed through a fixing nip formed between the pressure roller and the heating member with a film interposed therebetween, whereby the toner image T is heated and pressed to record. The fixing is performed on the material P.

Pressure Roller 7 According to Preferred Embodiment
Reference numeral 06 denotes a heat-resistant elastic layer coated with a silicone foam having a length of 240 mm, a thickness of 3 mm, and a thermal conductivity of 0.20 W / m · k on an aluminum core bar having an outer diameter of 13 mm connected to a driving device. Have been. The measurement of the thermal conductivity was performed using a rapid thermal conductivity meter QMT-500 manufactured by Kyoto Electronics Industry Co., Ltd. The object to be measured was measured using an actual pressure roller.

The heat conductivity of the heat-resistant elastic layer was 0.20 W /
m · k or less, and by using the pressure roller of the present embodiment, heat is less likely to be taken away by the pressure roller itself, and the heating start-up time can be shortened. In addition, excessive power consumption is eliminated, and the fixing property is improved immediately after the power is turned on. The material used for the heat-resistant elastic layer coated on the pressure roller is fluoro rubber,
Silicone rubber, silicone rubber foam, melamine foam, and silicone foam are preferably used, and more preferably silicone rubber foam, melamine foam, and silicone foam.

Next, the electrostatic image carrier used in the present invention will be described.

The surface layer of the electrostatic image carrier according to the present invention has the following formula (1):

[0146]

[Outside 18]

[0147] wherein, X ₁ is -CR ₁₃ R ₁₄ - (wherein R
₁₃ and R ₁₄ are each independently a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted α,
ω-alkylene group, single bond, -O-, -S-, -SO
— Or —SO ₂ —, and R _{1 to} R ₁₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]
Or a polyarylate resin having a structural unit represented by the following formula (2):

[0148]

[Outside 19]

[Wherein X ₂ is -CR ₂₃ R _24- (where R
₂₃ and R ₂₄ are each independently a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted α,
ω-alkylene group, single bond, -O-, -S-, -SO
— Or —SO ₂ —, and R _{15 to} R ₂₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. It is desirable to contain at least one of the polycarbonate resins having the structural unit represented by the formula (1).

The polyarylate resin having the structural unit represented by the formula (1) and the polycarbonate resin represented by the formula (2) used in the present invention must be capable of imparting appropriate abrasion. Specifically, it has a weight-average molecular weight of 7500 to 37000 and 10,000 to 3
It preferably has a weight average molecular weight of 7000,
More preferably, it has a weight average molecular weight of 500 to 30,000. If the weight average molecular weight is less than 7500, the strength is too large to cause damage due to repeated use, and further, the effect on image deletion is insufficient due to the influence. The weight average molecular weight is 37000
If it is larger, it is not possible to impart a suitable abrasion property, and the effect on image deletion becomes insufficient. The degree of dispersion of these resins is preferably 3.0 or less, more preferably 2.
It is preferably 6 or less. When the degree of dispersion is greater than 3.0, the proportion of those having a smaller molecular weight increases, causing a decrease in strength. As a result, scratches are liable to be caused by repeated use, and further, the effect on image deletion due to the effect is also reduced. Tends to be insufficient. The “dispersion degree” here is a value represented by weight average molecular weight / number average molecular weight.

The molecular weight in the present invention is measured by GPC (gel permeation chromatography) using polystyrene as a standard substance. Examples of more detailed measurement conditions are shown below. Apparatus: HLC-8120 (manufactured by Tosoh Corporation) Column: TSKgel Super HM-M 6 mm D. × 15 cm (manufactured by Tosoh Corporation) 2 standard substances: polystyrene (manufactured by Tosoh Corporation) Sample: 1 part by mass of resin / 1000 parts by mass of tetrahydrofuran Flow rate: 0.6 ml / min Solvent: tetrahydrofuran Temperature: 40 ° C. Detector: R. I, UV (254 nm) In formulas (1) and (2), a methyl group as an alkyl group,
Examples include an ethyl group, a propyl group, a cyclohexyl group and a cycloheptyl group. Examples of the aryl group include a phenyl group, a naphthyl group and an anthryl group.
As the cycloalkylidene group, a cyclohexylidene group,
And a cycloheptylidene group and a fluorenylidene group. Examples of the α, ω-alkylene group include a 1,2-ethylene group, a 1,3-propylene group, and a 1,4-butylene group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the substituent which these groups may have include halogen atoms such as fluorine, chlorine and bromine; alkyls such as methyl, ethyl and propyl; phenyl, naphthyl and anthryl. Aryl groups such as benzyl group and phenethyl group; and alkoxy groups such as methoxy group, ethoxy group and propoxy group.

The "single bond" means that the benzene rings on both sides of X1 or X2 are directly bonded. For example, the structural unit examples (1) -7, (1) -23 and (1) )
-24.

Tables 1 to 4 show specific examples of the structural units of the polyarylate resin having the structural unit represented by the formula (1) used in the present invention, but the present invention is not necessarily limited thereto.

[0155]

[Table 1]

[0156]

[Table 2]

[0157]

[Table 3]

[0158]

[Table 4]

Preferred examples are structural unit examples (1)-
1, (1) -2, (1) -3, (1) -4, (1) -9
And especially the structural units (1) -1, (1) -2,
(1) -4 is preferred.

The polyarylate resin having a constitutional unit represented by the formula (1) used in the present invention is usually a terephthalic acid chloride or an isophthalic acid chloride to improve the solubility of a bisphenol represented by the following formula (3). It can be synthesized by stirring the mixture and an alkali in a solvent / water system and performing interfacial polymerization.

[0161]

[Outside 20]

[0162] wherein, X ₁ is -CR ₁₃ R ₁₄ - (wherein R
₁₃ and R ₁₄ are the same or different and are a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted group; Α, ω-alkylene group, a single bond, -O-, -S-,
—SO— or —SO ₂ —. R _{1 to} R ₈ are the same or different and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The ratio of terephthalic acid chloride and isophthalic acid chloride is determined in consideration of the solubility of the polymer, and there is no standard. However, if any chloride is 3
Care must be taken when the content is 0 mol% or less, since the solubility of the synthesized polymer is extremely reduced. Usually, it is preferable to synthesize at a ratio of 1/1.

Further, in the electrostatic image carrier of the present invention, even if a polymer composed of the same structural unit represented by the formula (1) is used, two or more different types represented by the formula (1) may be used. Copolymers composed of structural units may be used. Furthermore, equation (1)
You may blend two or more types of resin which has a structural unit shown by these.

Preferred examples of the structural unit of the polycarbonate resin having the structural unit represented by the formula (2) used in the present invention are shown in Tables 5 to 8, but are not limited thereto.

[0165]

[Table 5]

[0166]

[Table 6]

[0167]

[Table 7]

[0168]

[Table 8]

Particularly preferred examples of the structural units (2) -1, (2) -2, (2) -3, (2) -4,
(2) -9, in particular, the structural unit (2) -1,
(2) -2 and (2) -4 are preferred.

The polycarbonate resin having a structural unit represented by the formula (2) used in the present invention is synthesized by polymerizing a bisphenol represented by the following formula (4) in the presence of phosgene usually in the presence of an alkali. be able to.

[0171]

[Outside 21]

[Wherein X ₂ is -CR ₂₃ R _24- (where R
₂₃ and R ₂₄ are the same or different and are a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted group; Α, ω-alkylene group, a single bond, -O-, -S-,
—SO— or —SO ₂ —. Also, R _{15 to} R ₂₂
Is the same or different and is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. In the electrostatic image carrier used in the present invention, even if the polymer is composed of the same structural unit represented by the formula (2), two or more kinds of different structural units represented by the formula (2) May be used. Furthermore, two or more of these resins may be blended, or may be blended with the resin represented by the formula (1).

The electrostatic image carrier used in the present invention may be mixed with a resin having a relatively large molecular weight, if necessary, for maintaining the film strength. As the resin to be used, a polyarylate resin represented by the formula (1) or a polycarbonate resin represented by the formula (2) is preferable. Specifically, the molecular weight of the resin preferably has a weight average molecular weight greater than 37000, Especially 5
It preferably has a weight average molecular weight of 0000 to 300,000.

Further, if necessary, it may be used by mixing with other resins. However, 7.5 × 10 ^{3 to} 3.7 × 10 ⁴
When mixing the resin of the present invention having a weight average molecular weight of other resins with the resin of the present invention, the resin of the present invention is preferably contained in an amount of 20% by mass or more, and more preferably 30% by mass or more based on the whole binder resin. More preferably.
When the amount is less than 20% by mass, it is difficult to impart a suitable abrasion, and the effect on image deletion tends to be insufficient.

The electrostatic image carrier used in the present invention includes
More preferably, the surface layer contains fluororesin particles. As fluororesin particles, tetrafluoroethylene resin, trifluoroethylene resin, hexafluoropropylene resin,
Vinyl fluoride resin, vinylidene fluoride resin, difluoride 2
It is desirable to appropriately select one or two or more selected from ethylene chloride resins and copolymers thereof, and particularly preferred are tetrafluoroethylene resins and vinylidene fluoride resins. The molecular weight of the resin can be appropriately selected and is not particularly limited.

The content of the fluororesin particles is 0.1 to 50% by mass based on the total solid weight in the layer containing the particles.
Is suitable, and particularly preferably 0.2 to 30% by mass. When the content is less than 0.1% by mass, the modifying effect by the dispersion of the fluororesin particles is not sufficient. On the other hand, when the content exceeds 50% by mass, the long-term stability of the coating material is deteriorated, the light transmittance is reduced, and This causes a decrease in mobility.

In the present invention, the primary particle size of the fluororesin particles is 0.3 μm or less, preferably 0.05 to 500 μm.
The thickness is preferably 0.3 μm, more preferably 0.08 to 0.3 μm. 0.3μ primary particle size of fluorine resin particles
If it is greater than m, the electrostatic image carrier according to the present invention uses a binder resin having a relatively low molecular weight, so that sedimentation of the fluorine-based resin particles in the coating solution tends to occur, and the long-term stability of the coating material The adverse effect that the properties and coating properties are deteriorated occurs. Primary particle size of fluorine resin particles is 0.05μm
If it is less than the above range, it becomes difficult to obtain the effect of adding the particles.

In order to improve the dispersibility of the fluorine-based resin particles, it is more preferable to use a fluorine-based comb-type graft polymer. The fluorine-based comb-type graft polymer has a molecular weight of 1000 having a polymerizable functional group at one end of each molecular chain.
It is obtained by copolymerizing an oligomer having a relatively low molecular weight of about 10000 and a fluoropolymerizable monomer,
It has a structure in which a macromonomer polymer is hung in a branch shape on a fluorine-based polymerizable trunk. As the macromonomer, those having an affinity for the resin to which the graft monomer is added are selected, and for example, polymers or copolymers of acrylates, methacrylates, styrene compounds, and the like are used.

On the other hand, as the fluorine-based polymerizable monomer,
One or more polymerizable monomers having a fluorine atom in the side chain as shown in Table 9 are used, but are not limited thereto.

[0180]

[Table 9]

In the formula, Ra represents _a hydrogen atom or a methyl group. R _b represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a nitrile group, and may be a combination of several kinds thereof. n is an integer of 1 or more, m is an integer of 1 to 5,
k represents an integer of 1 to 4, and m + k = 5.

In the formula of Table 9, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclohexyl group and a cycloheptyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

The content of the fluorine-based monomer residue in the fluorine-based comb-type graft polymer is preferably from 5 to 90% by mass in the fluorine-based comb-type graft polymer.
% By mass is more preferred. If the content of the fluorine-based monomer residue is less than 5% by mass, the effect of improving the hydrophobicity cannot be sufficiently exhibited, and if the content of the fluorine-based monomer residue exceeds 90% by mass, the solubility with the macromonomer is reduced. become worse.

The content of the fluorine-based comb type graft polymer is 0.01 to 20% based on the weight of the fluorine-based resin particles.
Is particularly preferable, and 0.1 to 10% is particularly preferable. 0.01
%, The effect of modifying the dispersibility of the fluororesin particles is not sufficient. On the other hand, if it exceeds 20%, the graft polymer is also present in the bulk of the coating film, so that the compatibility with the resin may cause a problem. When an electrophotographic process is performed, accumulation of residual potential occurs.

In the electrostatic image bearing member of the present invention, it is more preferable to add an antioxidant as needed. By adding an antioxidant, it is possible to suppress the oxidative deterioration of the surface deposits and the binder resin, which is the main cause of image deletion, and thus it is possible to more effectively prevent the image deletion.

As the antioxidant used in the present invention, hindered phenol antioxidants and phosphorus antioxidants are particularly preferable. These may be used alone, but it is particularly preferable to use a combination of a hindered phenol antioxidant and a phosphorus antioxidant.

If the content of the antioxidant is too small, the effect on image deletion will be insufficient, while if it is too large, electrophotographic characteristics such as an increase in residual potential will be deteriorated, so it is necessary to select an appropriate amount. is there. Specifically, 0.01 to resin
% By mass to 30% by mass is preferred, and especially 0.1% by mass to 2% by mass.
0% by mass is preferred.

Next, an electrophotographic photosensitive member, which is a typical example of the electrostatic image carrier used in the present invention, will be described.

The electrophotographic photoreceptor contains a charge transporting layer containing a charge transporting material and a charge generating material even if the photosensitive layer is a single layer type containing a charge transporting material and a charge generating material in the same layer. Although a laminated type separated into a charge generation layer may be used, a laminated type is preferable in terms of electrophotographic characteristics. Further, it is preferable that a charge transport layer is provided on the charge generation layer, and the charge transport layer is a surface layer. Hereinafter, this embodiment will be described as an example.

The conductive support to be used may be any one having conductivity, such as metal such as aluminum and stainless steel, or metal provided with a conductive layer, paper, plastic, and the like. And the like.

When the exposure is coherent light, a conductive layer may be provided on the conductive support for the purpose of preventing interference fringes due to scattering or covering a damage on the support. The conductive layer can be formed by dispersing conductive powder such as carbon black and metal particles in a binder resin. The thickness of the conductive layer is 5 to 4
0 μm, preferably 10 to 30 μm is suitable.

An intermediate layer having an adhesive function may be provided between the conductive support and the photosensitive layer. Examples of the material of the intermediate layer include polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, and polyether urethane. These are applied by dissolving in an appropriate solvent. The thickness of the intermediate layer is 0.05 to 5μ.
m, preferably 0.3 to 1 μm.

The charge generation layer contains a charge generation material of 0.3 to 4
By applying a homogenizer, ultrasonic dispersion, ball mill, vibrating ball mill, sand mill, attritor, roll mill and liquid collision type high-speed disperser together with a double amount of a suitable resin and solvent, a well-dispersed dispersion and drying. It is formed.

The charge generating materials used include selenium-tellurium, pyrylium, thiapyrylium dyes, phthalocyanines, anthantrones, dibenzopyrene quinones,
Examples include trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine pigments. The thickness of the charge generation layer is 5 μm or less, preferably 0.1 to 2 μm.

The charge transport layer is formed by applying and drying a coating liquid in which a charge transport material, the resin of the present invention and the fluorine-containing resin particles are dissolved and dispersed in a solvent. As a method of preparing the coating liquid, a charge transport material, a method of simultaneously dissolving and dispersing the resin of the present invention and the fluorine-containing resin particles in a solvent, and a coating liquid in which the resin and the fluorine-containing resin particles are previously dissolved and dispersed. And a method in which the charge transport material is prepared and mixed with a coating solution in which the charge transport material is dissolved. In the preparation of the coating liquid, it may be simple stirring and mixing, but if necessary, using a dispersing means such as a ball mill, a roll mill, a sand mill and a high-pressure disperser, so that the primary particles of the fluorine-containing resin particles are 0.3 μm or less. Mix.

Examples of the charge transporting material used include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, triarylmethane compounds, and thiazole compounds. These charge transporting materials are from 0.5 to
Combined with twice the amount of resin. The thickness of the charge transport layer is 5
４０40 μm, preferably 15-30 μm is suitable.

Next, an example of an image forming apparatus is schematically shown in FIG. 12, and an image forming method will be described based on the example.

Reference numeral 501 denotes a drum-shaped electrostatic latent image carrier, around which a charging roller (charging member) 502 of primary charging means, an exposure optical system 503, and a toner carrier 50 are provided.
5, a developing unit 504, a transfer unit 509, and a cleaning unit 511 are disposed.

In this image forming apparatus, the surface of the electrostatic latent image carrier 501, which is a photosensitive member, is uniformly charged by the charging roller 502, and is then exposed by the exposure optical system 503 to expose the electrostatic latent image carrier 501. To form an electrostatic latent image on the surface of the substrate.

The shape of the charging member used in the present invention is not particularly limited as long as it is a contact charging member which is arranged in contact with the electrostatic image carrier, and may be a roller shape, a blade shape, a brush shape, or the like. Any one may be used.

The voltage applied to the charging member is preferably such that the DC voltage has an absolute value of 200 to 2000 V, and the AC voltage has a peak-to-peak voltage of 400 to 4000 V.
Preferably, the frequency is between 200 and 3000 Hz.

Next, the toner carrier 50 containing a magnet
5, a toner coat layer is formed by a toner layer thickness regulating member 506, and the electrostatic latent image carrier 5 is formed in a developing section.
The electrostatic latent image formed on the electrostatic latent image carrier 501 is developed while applying an alternate bias, a pulse bias, and / or a DC bias by the bias applying means 508 between the conductive substrate No. 01 and the toner carrier 505. I do. In the figure, 50
Reference numeral 7 denotes a stirring unit, and 513 denotes a magnetic toner.

The developed toner image is transferred to a transfer sheet P, and a transfer roller 509 as a transfer means and a voltage applying means 51
As a result, a charge having a polarity opposite to that of the toner is applied from the rear surface of the transfer paper P, and the transfer paper P is electrostatically transferred to the transfer paper P.

The transfer paper P on which the toner image has been transferred passes through the heating / pressing roller fixing device 512, and the toner image becomes a fixed image.

The toner remaining on the latent image carrier after the transfer step is removed by a cleaning blade 511 as a cleaning means and collected by a cleaner 514.
The steps following the primary charging are repeated again.

In the present invention, a process cartridge is constructed by integrally combining a plurality of components such as the drum-shaped electrostatic image carrier, the developing device and the cleaning means as an apparatus unit. The process cartridge may be configured to be detachable from the apparatus main body. For example, a process cartridge is formed by integrally supporting the charging member and the developing device together with the electrostatic image carrier,
A single unit that is detachable from the apparatus main body may be used, and the unit may be detachable using a guide unit such as a rail of the apparatus main body. At this time, the above process cartridge may be provided with a cleaning unit.

FIG. 15 shows an embodiment of the process cartridge of the present invention. In this embodiment, the developing unit 50
4. Drum-shaped electrostatic image carrier (photosensitive drum) 50
1. Cleaner 5 having cleaning blade 511
14, a process cartridge 516 in which the primary charging member 502 is integrated. In this process cartridge, when the magnetic toner 513 of the developing unit 504 runs out, it is replaced with a new cartridge.

In this embodiment, the developing means 504 holds the magnetic toner 513, and a predetermined electric field is formed between the electrostatic image carrier 501 and the developing sleeve 505 as a toner carrier during development. . In order for the developing step to be performed properly, the electrostatic image carrier 501 and the developing sleeve 5
The distance to 05 is very important.

In the process cartridge shown in FIG. 15, the developing means 504 includes a toner container 515 for storing the magnetic toner 513 and the magnetic toner 513 in the toner container 515 from the toner container 515 to the electrostatic image carrier 501.
Sleeve 50 which is carried and transported to the development area facing the
5 and an elastic blade 506 as a toner layer thickness regulating member for regulating the magnetic toner conveyed to the developing area to a predetermined thickness and forming a thin toner layer on the developing sleeve.

The developing sleeve 505 can have any structure. Usually, it is composed of a non-magnetic developing sleeve 505 containing a magnet (not shown). Developing sleeve 505
May be a cylindrical rotating body as shown. It is also possible to adopt a belt shape that moves in a circulating manner. Usually, aluminum or SUS is preferably used as the material.

The elastic blade 506 is made of a rubber elastic material such as urethane rubber, silicone rubber or NBR; a metal elastic material such as phosphor bronze or a stainless steel plate; a resin elastic material such as polyethylene terephthalate or high density polyethylene. It is composed of boards. Elastic blade 506
Is the developing sleeve 505 due to the elasticity of the member itself.
And is fixed to the toner container 515 by a blade support member made of a rigid body such as iron. Elastic blade 506
Is a linear pressure of 4.9-78.4 N / m (5-80 g / cm)
, It is preferable to abut in the counter direction with respect to the rotation direction of the developing sleeve 505. Instead of the elastic blade 506, it is also possible to use a magnetic doctor blade such as iron.

The primary charging means has been described using the charging roller 502 as a contact charging member, but may be a contact charging means such as a charging blade or a charging brush. This contact charging member is preferable in that generation of ozone due to charging is small. The transfer means has been described using the transfer roller 509, but may be a contact charging means such as a transfer blade.
Further, a non-contact corona transfer unit may be used, but a contact charging unit is preferable because ozone is less generated by transfer.

When the image forming method of the present invention is applied to a facsimile printer, the light image exposure L is an exposure for printing received data. FIG. 13 is a block diagram showing an example of this case.

The controller 631 controls the image reading section 630 and the printer 639. The whole controller 631 is controlled by the CPU 637. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 633. Data received from the partner station is sent to the printer 639 through the receiving circuit 632. Predetermined image data is stored in the image memory. Printer controller 6
38 controls the printer 639. 634 is a telephone.

The image received from the line 635 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 632, and then the CPU 637 performs a decoding process on the image information and sequentially executes the image memory 636. Is stored in When the image of at least one page is stored in the memory 636, the image of the page is recorded. CPU 637
Reads out one page of image information from the memory 636 and sends the combined one page of image information to the printer controller 638. The printer controller 638 uses C
When receiving the image information of one page from the PU 637, the printer 639 is controlled to record the image information of the page.

The CPU 637 receives the next page during recording by the printer 639.

As described above, image reception and recording are performed.

[0218]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples. “Parts” means parts by mass.

Example 1 First, the preparation of a toner will be described. 100 parts of binder resin (styrene resin) 100 parts of magnetic substance (Fe ₃ O ₄ ) 2 parts of charge control agent (monoazo iron complex) 4 parts of wax W1 (polypropylene wax, melting point 143 ° C.) 4 parts ・ wax W2 ( (Paraffin wax, melting point: 75 ° C.) 3 parts The above mixture was melt-kneaded by a biaxial extruder heated to 130 ° C., and the cooled kneaded product was roughly pulverized by a hammer mill.

The coarsely pulverized product was pulverized and classified by an apparatus system shown in FIG. As the mechanical pulverizer 301, a turbo mill T-250 type manufactured by Turbo Kogyo Co., Ltd. is used, the gap between the rotor 314 and the stator 310 shown in FIG. 3 is 1.5 mm, and the peripheral speed of the rotor 314 is 115 m / s. I drove.

In the present embodiment, the powdery raw material composed of the coarsely pulverized material was 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 (the swirl chamber temperature T1) in the mechanical pulverizer was −10 ° C., and the outlet temperature (the rear room temperature T2) was 4 ° C.
At 6 ° C., ΔT of T1 and T2 was 56 ° C. The finely pulverized product obtained by pulverization with the mechanical pulverizer 301 at this time has a weight average diameter of 6.5 μm and a particle diameter of 4.00 μm.
The following particles had a sharp particle size distribution containing 41.8% by number and 3.6% by volume of particles having a particle size of 10.1 μm or more.

Next, the finely pulverized product obtained by the pulverization by the mechanical pulverizer 301 is introduced into the second quantitative feeder 2,
44k via vibration feeder 3 and material supply nozzle 16
The g / h ratio 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. When introducing into the airflow classifier 1, the outlet 11,
The pressure in the classification chamber is reduced through at least one of 12 and 13, and an air flow flowing through the raw material supply nozzle 16 having an opening in the classification chamber by the reduced pressure and compressed air injected from the high-pressure air supply nozzle are used. . The introduced finely pulverized product was instantaneously classified into three types of coarse powder, medium powder and fine powder in 0.1 seconds or less. Among the classified materials, the coarse powder was collected by the collecting cyclone 6, introduced into the mechanical pulverizer 301 described above at a rate of 2.0 kg / h, and introduced again into the pulverizing step.

To 100 parts of the obtained intermediate powder, 1.2 parts of hydrophobic silica fine powder and 0.5 part of strontium titanate fine powder were added and mixed with a Henschel mixer to obtain a toner. Table 1 shows the circularity and DSC characteristics of this toner.
0.

Further, the preparation of the electrostatic image carrier (hereinafter referred to as "photosensitive drum") used in this embodiment will be described.

A 30φ, 254 mm aluminum cylinder was used as a support, and a coating solution composed of the following material was applied on the aluminum cylinder by a dipping method, and thermally cured at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 15 μm. A layer was formed. Conductive pigment (SnO ₂ coating process of barium sulfate) 10 parts resistance adjusting pigment (titanium oxide) 2 parts Binder resin (phenol resin) 6 parts Leveling material (silicone oil) 0.001 parts Solvent 20 parts ( Methanol / methoxypropanol; 0.2 / 0.8
[Mass ratio]) Next, 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon were added thereto with 65 parts of methanol /
A solution dissolved in a mixed solvent of 30 parts of n-butanol is applied by a dipping method, and dried to have a thickness of 0.5 μm.
Was formed.

Next, the diffraction angles 2θ ± 0.2 ° in the X-ray diffraction spectrum of CuKα are 9.0 °, 14.2 °, 2 °
4 parts of oxytitanium phthalocyanine (TiOPc) having strong peaks at 3.9 ° and 27.1 °, 2 parts of polyvinyl butyral (trade name: Eslec BM2, manufactured by Sekisui Chemical) and 60 parts of cyclohexanone were used for φ1 mm glass beads. The mixture was dispersed for 4 hours using a sand mill. Thereafter, 100 parts of ethyl acetate was added to prepare a charge generation layer dispersion. This was applied by dipping and dried to form a charge generating layer having a thickness of 0.3 μm on the intermediate layer.

Next, 9 parts of an amine compound represented by the following formula:

[0228]

[Outside 22]

One part of an amine compound represented by the following formula:

[0230]

[Outside 23]

10 parts of the binder resin (No. 1) of Structural Unit Example (2) -2 was dissolved in a mixed solvent of 50 parts of monochlorobenzene / 50 parts of dichloromethane. The weight average molecular weight of this resin was 50,000.

This coating solution was applied by a dipping method,
For 2 hours to form a charge transport layer having a thickness of 25 μm on the charge generation layer.

As the image forming apparatus shown in FIG. 12, the process speed was modified to 55 mm / sec using an LBP “LJ-6L” manufactured by Hewlett-Packard Company, and the fixing unit was further modified to the configuration shown in FIG. The vessel was designated as T2. Here, regarding the pressure roller, a core metal outer diameter φ13 mm, a heat-resistant elastic layer, a silicone rubber thickness of 3 mm, a release layer, a fluorine rubber, a thickness of 50 μm, a two-layer structure, and a thermal conductivity of a heat-resistant elastic layer and a release layer of 0. 3 W / m · k. The photosensitive drum D1 and the toner were set in the process cartridge of the modified model "LJ-6L", and the evaluation was performed according to the following image evaluation method.

The modified model "LJ-6L" uses, as a primary charging member, a contact charging roller which is in contact with the surface of the photoreceptor. DC voltage: -625 V, AC voltage: peak-to-peak voltage 1. The image forming apparatus has a configuration in which a charging voltage of 8 kV and a frequency of 370 Hz is applied to primary charge the photosensitive member.

The image evaluation was performed as follows.

(1) Fixing Property The fixing property was determined after the main unit power was turned on when the fixing device was sufficiently cooled in a low-temperature and low-humidity environment (7.5 ° C., 10% RH).
4.9 × 10 ^-3 MP for the image fixed and printed on the sheet
a, and rub the fixed image with soft thin paper,
The worst value of the rate of decrease (%) in image density before and after rubbing was evaluated. Test paper is Plover Bond (90 g / m ² )
It was used. A (excellent): less than 5% B (good): 5 to 10% C (acceptable): 10 to 20% D (poor): 20% or more (2) Offset resistance The offset resistance is a half-solid black sample. The image was printed out and evaluated based on the degree of stain on the unprinted solid white portion on the image. Plain paper for copying machines (64 g / m ² ) was used as test paper. A (excellent): not generated B (good): hardly generated C (acceptable): slightly generated (no problem in practical use) D (bad): dirty (3) dirt on pressure roller 10 minutes, 2
Sheet intermittent mode image output, Boise Cascade X-9000 as test paper, 1000, 200 in a low temperature and low humidity environment (15 ° C., 10% RH)
The degree of toner contamination on the members inside the fixing device and the image at the end of printing out 0, 3000 sheets was visually evaluated. A (excellent): there is no dirt on the pressure roller and there is no dirt on the image B (good): there is almost no dirt on the pressure roller and there is no dirt on the image C (good): dirt on the pressure roller There is a dirt on the image, but there is no dirt D (bad): Dirt on the pressure roller and dirt on the image (4) Drum fusion High temperature and high humidity environment (33.0 ° C., 95% RH) At
After continuous printing of 2500 sheets of an image having an image area ratio of about 3%, a solid black image was formed on the entire surface of an A4 size recording paper, and the degree of white spots generated on the solid black image was evaluated. A: No white spot is generated on A4 size recording paper. C: About 10 white spots are observed on A4 size recording paper. E: 100 or more white spots are observed on A4 size recording paper.

Note that B is an intermediate level between A and C, and D is an intermediate level between C and E.

(5) Image deletion In a high temperature / high humidity environment (33.0 ° C., 95% RH)
An image having an image area ratio of about 3% was continuously printed out on 2500 sheets, and evaluated by the degree of image deletion after 2500 sheets. In this evaluation, experience has shown that paper (33.0 ° C., 95%
The sheet having a moisture absorption of 10% under RH) was used as an evaluation sheet.
In addition, the amount of moisture absorption of the paper is measured by Infrared Engineer.
It was measured using MOISTREX MX 5000 manufactured by Ring. A: No image deletion occurs. C: Image deletion has occurred, but what character is can be determined. E: Image deletion occurs, and it is not possible to determine what characters are.

Note that B is an intermediate level between A and C, and D is an intermediate level between C and E.

<Example 2> A toner obtained in the same manner as in Example 1 was used, and the pressure roller was changed to a core metal outer diameter of 13 m.
m, heat-resistant elastic layer: silicone rubber foam, thickness 3 mm,
The same procedure as in Example 1 was carried out except that the fixing device T1 was modified to have a single-layer structure and a heat-resistant elastic layer having a thermal conductivity of 0.1 W / m · k. Table 10 shows the results.

<Example 3> As the resin of the charge transport layer, 4 parts (40% by mass of the whole resin) of resin (No. 2) of Structural Unit Example (2) -2 (weight average molecular weight 12000) were used. A photosensitive drum D2 was produced in the same manner as in Example 1, except that 6 parts (60% by mass of the whole resin) of the resin (No. 3) of (2) -2 (weight average molecular weight: 50,000) was used.
Image evaluation was performed using the same toner and fixing device as in Example 1. Table 10 shows the results.

<Comparative Example 1> The same fixing device and photosensitive drum as in Example 1 were used. With respect to the toner, the crushed material obtained in the same manner as in Example 1 except that only the wax of W1 was used was crushed and classified by the apparatus system shown in FIGS. However, the impingement type air current pulverizer uses the pulverizer shown in FIG. 10, the first classifier (52 in FIG. 8) has the structure shown in FIG. 9, and the second classifier (57 in FIG. 8). 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 is provided on a partition wall between the classifying chamber 404 and the guide chamber 405, and the powder material and the air fed 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 a conical upper casing 413 and a conical upper cover 406.

A classifying 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 classifying chamber 404 is supplied to the classifying 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. In addition, a fine powder discharge chute 412 is connected to the center of the classification 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 or a dust collector, and the suction fan applies a suction force to the classifying chamber 404 to flow into the classifying chamber 404 from between the louvers 409. The swirling flow required for classification is caused by the suction air.

The air classifier of the first classifying means of this comparative example has the above-mentioned structure. When air containing the above-mentioned crushed material for toner production is supplied from the supply tube 408 into the guide chamber 405, the crushed material is removed. The contained air flows from the guide chamber 405 to the classifying chamber 404 while passing between the louvers 407 while flowing at a uniform concentration while being dispersed.

The crushed material which 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 at the lower part of the classifying chamber. The coarse powder which 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 outlet 411 and discharged from the lower hopper 403. You.

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 pulverized raw material is supplied at a rate of 13.0 kg / h to the airflow classifier shown in FIG. 9 at a rate of 13.0 kg / h by the first table-type fixed quantity feeder 121, and is stretched by centrifugal force acting on the particles. Classified by separation. The classified coarse powder is supplied through a coarse powder discharge hopper 403 from a pulverized material supply port 165 of the collision type air flow pulverizer shown in FIG. 10 and has a pressure of 0.6 MPa and 6.0 m ³ /.
After being pulverized using compressed air of min, while being mixed with the toner pulverization raw material supplied in the raw material introduction section, the mixture was circulated again to the airflow classifier to perform closed circuit pulverization. On the other hand, the classified fine powder was introduced into the second classification means 57 of FIG. 8 while being entrained by the suction air from the exhaust fan, and was collected by the cyclone 131.

The fine powder obtained by the collection is supplied to the vibration feeder 125 and the nozzle 148 through the second quantitative feeder 124.
And 149, the mixture was introduced into an air-flow classifier shown in FIG. 11 in order to classify three kinds of coarse powder, medium powder and fine powder utilizing the Coanda effect at a rate of 15.0 kg / h. At the time of introduction, a suction force derived from reduced pressure in the system due to 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 is collected by a collecting cyclone 129, and then collected by a collision type air current pulverizer 58 described above.
It was introduced at a rate of 8 kg / h and introduced again into the pulverizing step.

A toner obtained in the same manner as in Example 1 except that the classified product obtained by the above method was used.
Table 10 shows the evaluation results.

[0254]

[Table 10]

[0255]

According to the present invention, by using a toner having a specific circularity and a specific thermal characteristic, an image which is excellent in offset resistance and free from contamination of the pressure roller while maintaining good fixing performance can be obtained. It became possible to obtain.

Further, according to the present invention, by using an electrostatic image carrier having a specific molecular weight in the above-mentioned structure, the above-mentioned effect is achieved, and no image deletion occurs and no image fusion occurs on the drum. It has become possible to provide a forming method and an image forming toner.

[Brief description of the drawings]

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

FIG. 2 is a schematic view 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 view schematically showing an example of an image forming apparatus used in the image forming method of the present invention.

FIG. 13 is a block diagram when the image forming method of the present invention is applied to a facsimile printer.

FIG. 14 is a schematic cross-sectional view of a tensionless film heating type heat fixing device according to the present invention.

FIG. 15 is an explanatory view showing an embodiment of the process cartridge of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Multi-division classification apparatus 301 Mechanical pulverizer 501 Electrostatic image carrier 502 Primary charging apparatus 503 Exposure optical system 504 Developing apparatus 505 Toner carrier 506 Toner layer thickness regulating member 507 Toner stirring means 508 Developing bias power supply 509 Transfer apparatus 510 Transfer Current generator 511 Cleaning means 512 Fixing device 513 Toner 516 Process cartridge 701 Stay 702 Heat resistant film 703 Heating body 706 Pressure roller T Toner P Transfer material (recording material)

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03G 5/147 502 G03G 5/147 502 9/087 9/08 381 F term (Reference) 2H005 AA06 AB04 CA14 DA06 DA10 EA03 EA05 EA10 2H068 AA13 AA21 BB26 BB27 BB52 FA27 4D021 FA24 FA26 GA02 GA03 GA08 GA11 GA16 GA18 HA01 HA10 4D065 AA07 BB01 BB11 EB14 EB20 ED02 ED14 ED24 ED27 ED32 EE13

Claims (16)

[Claims] 1. A toner containing at least a binder resin, a magnetic substance and a wax, wherein a particle having a particle size of 3 μm or more has a circularity a obtained by the following formula (A).
Are 90% or more in terms of the number-based cumulative value of particles having a number of 0.900 or more, and particles having a circularity a of 0.950 or more are present in a number-based cumulative value of 67% or more, and the circularity a Is present in a number-based cumulative value of 8% or more, and the circularity a of the particles having a circularity a of 0.995 or more is 0.950 or more. 12% or more of the cumulative value (In the formula, L ₀ represents the peripheral length of a circle having the same projected area as the particle image, and L represents the peripheral length of the particle image.) Endothermic curve at the time of temperature rise in DSC measurement of the toner by a differential scanning calorimeter Wherein the toner has an endothermic peak in a temperature range of 50 ° C. to 120 ° C. and a temperature range of more than 120 ° C. to 180 ° C., respectively. 2. The toner according to claim 1, wherein said toner is a DS
A wax A having a maximum endothermic peak in a temperature range of 50 ° C. to 120 ° C. in an endothermic curve at the time of temperature rise in C measurement;
2. The toner according to claim 1, further comprising a wax B having a maximum endothermic peak in a temperature range of more than 120 ° C. to 180 ° C. 3. 3. The kneaded product obtained by melting and kneading a mixture containing at least a binder resin and a magnetic material, wherein the toner is produced through a melt kneading step, a fine pulverizing step and a classification step. After cooling, the cooled material is coarsely pulverized by a pulverizing means, and the obtained powdery raw material of the coarsely pulverized material is introduced into a first constant-volume feeder, and at least a rotor which is a rotating body attached to a central rotating shaft. And a stator disposed around the rotor while maintaining a constant interval with the rotor surface, and the annular space formed by maintaining the interval is configured to be airtight. A predetermined amount of powder raw material is introduced into the mechanical pulverizer through the powder inlet of the mechanical pulverizer from the first metering device, and the rotor of the mechanical pulverizer is rotated at a high speed. The powder raw material is finely pulverized by The pulverized material is discharged from the powder discharge port of the mechanical pulverizer and introduced into the second metering device. A predetermined amount of the fine material is used from the second metering device, utilizing the crossed airflow and the Coanda effect. Into a multi-divided airflow classifier that classifies the powder into air, and classifies the finely pulverized product into at least fine powder, medium powder, and coarse powder in the multi-divided airflow classifier, and classifies the coarse powder. The toner according to claim 1, wherein the toner is a toner produced by mixing the powder with a raw material, introducing the powder into the mechanical pulverizer, pulverizing the powder, and classifying the powder. 4. The multi-divided air flow 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-divided air flow classifier, wherein the classification in the multi-divided air flow classifier is performed. Classification edge block with edge,
4. The toner according to claim 3, 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. 5. The toner charges an electrostatic image carrier for carrying an electrostatic image, forms an electrostatic image on the charged electrostatic image carrier, and charges the electrostatic image by the toner of the developing means. Developing the image to form a toner image, transferring the toner image on the electrostatic image carrier to a transfer material with or without an intermediate transfer member, and using a heat-resistant film and a heating element via the heat-resistant film 0.20W thermal conductivity arranged to be pressed against
By using a heat-fixing device that sandwiches and conveys the transfer material and applies thermal energy to the transfer material between the heat-resistant elastic layer and a pressure member having a heat-resistant elastic layer on the metal core of not more than / mk.
2. The toner according to claim 1, which is used in an image forming method for fixing a toner image on a transfer material to the transfer material. 6. The electrostatic image carrier according to claim 1, wherein the surface layer has
Formula (1) having a weight average molecular weight of 7.5 × 10 ^{3 to} 3.7 × 10 ⁴ Wherein, X1 is -CR ₁₃ R ₁₄ - (provided that R ₁₃ and R ₁₄
Is each independently a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted α, ω- Alkylene group, single bond, -O-, -S-, -SO-, or -S
O ₂ —, and R _{1 to} R ₁₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Or a polyarylate resin having a structural unit represented by the formula:
^{The following} formula (2) having a weight average molecular weight of ^{3 to} 3.7 × 10 ⁴ [Wherein, X ₂ is -CR ₂₃ R _24- (where R ₂₃ and R ₂₄
Is each independently a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted α, ω- Alkylene group, single bond, -O-, -S-, -SO-, or -S
O ₂ —, and R _{15 to} R ₂₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The toner according to claim 5, comprising at least one kind of a polycarbonate resin having a structural unit represented by the following formula: 7. An electrostatic image carrier for carrying an electrostatic image is charged, an electrostatic image is formed on the charged electrostatic image carrier, and the electrostatic image is developed by a toner included in a developing unit. To form a toner image, transfer the toner image on the electrostatic image carrier to a transfer material with or without an intermediate transfer member, and press against a heat-resistant film and a heating member via the heat-resistant film. Between the pressing member having a heat-resistant elastic layer having a thermal conductivity of 0.20 W / m · k or less and having a heat conductivity of 0.20 W / m · k or less on a cored bar. An image forming method in which a toner image on a transfer material is fixed to the transfer material by using a heat fixing device for imparting the toner, wherein the toner contains at least a binder resin, a magnetic material and a wax, and has a thickness of 3 μm. In the above particles, the value is obtained from the following formula (A). Particles having a circularity a of 0.900 or more have a cumulative number-based value of 90% or more, and particles having a circularity a of 0.950 or more have a cumulative number-based value of 67.
% Or more, and particles having a circularity a of 0.995 or more exist in a number-based cumulative value of 8% or more, and the circularity a
Is 0.995 or more, and the circularity a is 0.95.
It is present at 12% or more with respect to the cumulative value based on the number of particles of 0 or more. (In the formula, L ₀ represents the peripheral length of a circle having the same projected area as the particle image, and L represents the peripheral length of the particle image.) Endothermic curve at the time of temperature rise in DSC measurement of the toner by a differential scanning calorimeter Wherein the image forming method has an endothermic peak in a temperature range of 50 ° C. to 120 ° C. and a temperature range of more than 120 ° C. to 180 ° C., respectively. 8. The toner according to claim 1, wherein said toner is a DS
A wax A having a maximum endothermic peak in a temperature range of 50 ° C. to 120 ° C. in an endothermic curve at the time of temperature rise in C measurement;
The image forming method according to claim 7, further comprising: wax B having a maximum endothermic peak in a temperature range of more than 120 ° C to 180 ° C. 9. 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 and a magnetic material. After cooling, the cooled material is coarsely pulverized by a pulverizing means, and the obtained powdery raw material of the coarsely pulverized material is introduced into a first constant-volume feeder, and at least a rotor which is a rotating body attached to a central rotating shaft. And a stator disposed around the rotor while maintaining a constant interval with the rotor surface, and the annular space formed by maintaining the interval is configured to be airtight. A predetermined amount of powder raw material is introduced into the mechanical pulverizer through the powder inlet of the mechanical pulverizer from the first metering device, and the rotor of the mechanical pulverizer is rotated at a high speed. The powder raw material is finely pulverized by The pulverized material is discharged from the powder discharge port of the mechanical pulverizer and introduced into the second metering device. A predetermined amount of the fine material is used from the second metering device, utilizing the crossed airflow and the Coanda effect. Into a multi-divided airflow classifier that classifies the powder into air, classifies the finely pulverized material into at least fine powder, medium powder and coarse powder in the multi-divided airflow classifier, and classifies the coarse powder. 9. The image forming method according to claim 7, wherein the toner is a toner produced from a medium powder obtained by mixing the powder with a raw material, introducing the powder into the mechanical pulverizer, and pulverizing the powder. . 10. The multi-divided air flow 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-divided air flow classifier, and performs classification in the multi-divided air flow classifier. The image forming method according to claim 9, wherein the classification edge block having an edge is a multi-division airflow type classification machine whose position can be changed so that the shape of the classification area can be changed. 11. The electrostatic image carrier according to claim 11, wherein the surface layer has
Formula (1) having a weight average molecular weight of 7.5 × 10 ^{3 to} 3.7 × 10 ⁴ Wherein, X ₁ is -CR ₁₃ R ₁₄ - (provided that R ₁₃ and R ₁₄
Is each independently a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted α, ω- Alkylene group, single bond, -O-, -S-, -SO-, or -S
O ₂ —, and R _{1 to} R ₁₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Or a polyarylate resin having a structural unit represented by the formula:
Formula (2) having a weight average molecular weight of ^{3 to} 3.7 × 10 ⁴ [Wherein, X ₂ is -CR ₂₃ R _24- (where R ₂₃ and R ₂₄
Is each independently a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted α, ω- Alkylene group, single bond, -O-, -S-, -SO-, or -S
O ₂ —, and R _{15 to} R ₂₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The image forming method according to claim 10, comprising at least one kind of a polycarbonate resin having a structural unit represented by the following formula: 12. A process cartridge detachably mounted on a main body of an image forming apparatus, wherein the process cartridge carries an electrostatic image carrier for carrying an electrostatic image, and is carried on the electrostatic image carrier. Developing means for holding a toner for developing the electrostatic image to form a toner image, wherein the toner is a toner containing at least a binder resin, a magnetic substance, and a wax; Among particles having a particle size of 3 μm or more, particles having a circularity a of 0.900 or more determined by the following formula (A) have a cumulative value on a number basis of 90% or more, and a particle having a circularity a of 0.950 or more. It has a cumulative value of 67% or more based on the number, and the circularity a is 0.
995 or more particles exist in a number-based cumulative value of 8% or more, and the abundance of particles having a circularity a of 0.995 or more is reduced to the number-based cumulative value of particles having a circularity a of 0.950 or more. More than 12%, (In the formula, L ₀ represents the peripheral length of a circle having the same projected area as the particle image, and L represents the peripheral length of the particle image.) Endothermic curve at the time of temperature rise in DSC measurement of the toner by a differential scanning calorimeter Wherein the process cartridge has endothermic peaks in a temperature range of 50 ° C. to 120 ° C. and a temperature range of more than 120 ° C. to 180 ° C., respectively. 13. The toner according to claim 1, wherein the toner has a D
A wax A having a maximum endothermic peak in a temperature range of 50 ° C. to 120 ° C. in an endothermic curve at the time of temperature increase in SC measurement
13. The process cartridge according to claim 12, comprising: a wax B having a maximum endothermic peak in a temperature range of more than 120 ° C. to 180 ° C. 14. The kneaded product obtained by melting and kneading a mixture containing at least a binder resin and a magnetic material, wherein the kneaded product is produced through a melt kneading step, a fine pulverizing step and a classification step. After cooling, the cooled material is coarsely pulverized by a pulverizing means, and the obtained powdery raw material of the coarsely pulverized material is introduced into a first constant-volume feeder, and at least a rotor which is a rotating body attached to a central rotating shaft. And a stator disposed around the rotor while maintaining a constant interval with the rotor surface, and the annular space formed by maintaining the interval is configured to be airtight. A predetermined amount of powder raw material is introduced into the mechanical pulverizer through the powder inlet of the mechanical pulverizer from the first metering device, and the rotor of the mechanical pulverizer is rotated at a high speed. By pulverizing the powder raw material, The finely pulverized material is discharged from the powder discharge port of the mechanical pulverizer and introduced into the second metering device. A predetermined amount of the finely pulverized material is crossed from the second metering device to reduce cross airflow and Coanda effect. The powder is introduced into a multi-divided airflow classifier that classifies the powder by air flow, and the finely pulverized material is classified into at least a fine powder, a medium powder, and a coarse powder in the multi-divided airflow classifier, and the classified coarse 14. The process cartridge according to claim 12, wherein the powder is mixed with a powder raw material, introduced into the mechanical pulverizer, pulverized, and classified into a toner generated from the classified medium powder. . 15. The multi-split air flow 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 air flow classifier, and performs classification in the multi-split air flow classifier. The process cartridge according to claim 14, wherein the classification edge block having an edge is a multi-divided airflow type classification machine whose position can be changed so that the shape of the classification area can be changed. 16. The electrostatic image carrier according to claim 16, wherein the surface layer is
Formula (1) having a weight average molecular weight of 7.5 × 10 ^{3 to} 3.7 × 10 ⁴ Wherein, X ₁ is -CR ₁₃ R ₁₄ - (provided that R ₁₃ and R ₁₄
Is each independently a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted α, ω- Alkylene group, single bond, -O-, -S-, -SO-, or -S
O ₂ —, and R _{1 to} R ₁₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Or a polyarylate resin having a structural unit represented by the formula:
Formula (2) having a weight average molecular weight of ^{3 to} 3.7 × 10 ⁴ [Wherein, X ₂ is -CR ₂₃ R _24- (where R ₂₃ and R ₂₄
Is each independently a hydrogen atom, a trifluoromethyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), a substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted α, ω- Alkylene group, single bond, -O-, -S-, -SO-, or -S
O ₂ —, and R _{15 to} R ₂₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The process cartridge according to any one of claims 12 to 15, comprising at least one kind of a polycarbonate resin having a structural unit represented by the following formula: