JP3093371B2 - Electrostatic image developing developer, image forming method, electrophotographic apparatus, apparatus unit, and facsimile apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer for developing an electrostatic latent image for visualizing an electrostatic latent image in an image forming method such as electrophotography, electrostatic recording and electrostatic printing, an image forming method, and an electrophotographic method. The present invention relates to an apparatus, an apparatus unit, and a facsimile apparatus.

More specifically, an electrophotographic method having a charging step of charging by bringing a charging member to which an external voltage is applied into contact with an electrostatic latent image holding member and a developing step of developing an electrostatic latent image using a developer. The present invention relates to a developer for developing an electrostatic latent image, an image forming method, an electrophotographic apparatus, an apparatus unit, and a facsimile apparatus used in the method.

[0003]

2. Description of the Related Art Conventionally, a corona discharger has been known as a charging means in an electrophotographic apparatus or the like. However, the corona discharger needs to apply a high voltage, and thus has a problem that a large amount of ozone is generated.

Recently, the use of contact charging means without using a corona discharger has been studied. Specifically, a voltage is applied to a conductive roller serving as a charging member, and the roller is brought into contact with a photosensitive member serving as a member to be charged, thereby charging the surface of the photosensitive member to a predetermined potential. If such a contact charging means is used, the voltage is reduced as compared with a corona discharger, and the amount of ozone generated is reduced.

For example, Japanese Patent Publication No. 50-13661 proposes charging a photosensitive paper by applying a low voltage to a photosensitive paper using a roller whose core is covered with a dielectric material made of nylon or polyurethane rubber. .

However, in the case of a roller in which the core metal is covered with nylon, since the roller does not have elasticity like rubber, the roller cannot maintain sufficient contact with the member to be charged, so that charging failure is likely to occur. On the other hand, when the core metal is coated with the polyurethane rubber, the softener impregnated in the polyurethane rubber exudes, and when the photoreceptor is used as the charged body, the roller is fixed to the photoreceptor at the contact portion when the photoreceptor stops. There is a problem that the image is easily blurred or the contact area thereof is blurred. When the softening agent in the rubber material of the roller exudes and adheres to the surface of the photoreceptor, the resistance of the photoreceptor decreases and the image flows (the charge of the electrostatic image leaks on the surface of the photoreceptor).
In a worst case, the toner cannot be used, or the toner remaining on the surface of the photoreceptor adheres to the surface of the roller, thereby causing a filming phenomenon. If a large amount of toner adheres to the roller surface, the roller surface becomes insulated, the charging ability of the roller is lost, the charging of the photoreceptor surface becomes uneven, and the image is affected.

The use of hydrophobic fine silica powder as an inorganic fine powder has been proposed in JP-A-46-5782, JP-A-48-47345, JP-A-48-47346, and the like. . For example, silica fine powder which has been hydrophobized by reacting silica fine powder with an organosilicon compound such as dimethyldichlorosilane to replace the silanol group on the surface of the silica fine powder with an organic group is used.

However, in a developer having such an inorganic fine powder, a contact charging member and a photosensitive member are particularly damaged in an image forming process in which the photosensitive member is pressed by contact charging. In the contact charging member and the photoconductor, toner fusion and filming are likely to occur. In extreme cases, image defects are likely to occur.

As for the addition of resin fine particles to a developer, Japanese Patent Application Laid-Open No. 60-186854 proposes to add a spherical or almost spherical polymer particle smaller than a toner particle to a developer. I have.

When a developer was prepared and examined in the same manner as above, it was found that the developer had little effect on preventing fusion of the toner on the photoreceptor, and in a device using contact charging, the contact charging device was contaminated.
Charging unevenness was likely to occur.

This is because the developer is strongly pressed against the surface of the photoreceptor by the charging member, so that the residual developer adheres to the charging member and the surface of the member to be charged, and furthermore, the surface of the charging member and the surface of the member to be damaged are damaged or scraped off. This is because it becomes easier.

In the contact charging means, a DC voltage or a DC voltage superimposed with an AC voltage is applied to the charging member and used. At this time, the particle diameter is particularly small around the contact portion between the charging member and the photosensitive drum. Abnormal charging of the light residual developer and repeated repetition of the flying motion are repeated, which makes it difficult for the residual developer to be electrostatically attracted and embedded on the charging member and the surface of the photosensitive drum. This is very different from the case where non-contact charging means using a corona discharger is used.

On the other hand, in recent years, small and inexpensive personal use copying machines and laser printers have emerged. In these small machines, from a maintenance-free standpoint, a cartridge system in which a photoconductor, a developing device, a cleaning device, and the like are integrated. It is desirable to use a magnetic one-component developer because the structure of the developing device can be simplified as the developer.

In such a method using a magnetic one-component developer, in order to form a visible image with good image quality, the developer must have high fluidity and uniform chargeability. It is necessary, and for that purpose, inorganic fine powder has conventionally been added to and mixed with toner powder.

Japanese Patent Application Laid-Open No. 1-121861 proposes a developer in which organic fine particles are added to toner particles containing an ion-crosslinked vinyl polymer as a binder resin. In the developer, spherical organic fine particles are preferred.

As a fixing method of a toner image, a contact heating method represented by a heating roller fixing method is generally used.
There is a demand for a toner that can be fixed at a low temperature in order to reduce power consumption.

For this reason, it has been proposed to incorporate a low molecular weight component and a high molecular weight component in a resin to improve low-temperature fixing and offset resistance.

However, when a developer containing a binder resin having an increased amount of low molecular weight for low-temperature fixing is used in an image forming apparatus having a contact charging device or a contact transfer means, the following problems tend to occur. .

If the low molecular weight component in the binder resin is large, the toner particles are good in pulverizability, so that the toner particles are easily chipped due to shearing in the production and in a developing device, etc., so that ultrafine particles are easily generated, and the contact charging member or the like is slid through the cleaner. It adheres to the contact transfer means and causes poor charging and poor transfer in a low-temperature and low-humidity environment, and easily fuses toner to the surface of the photoreceptor in a high-temperature and high-humidity environment.

Since the ultrafine particles lacking the toner particles have the same chargeability as the toner particles, they impede the charging of the toner particles and lower the image density.

In the contact heating method, it is required that the toner is surely softened and fixed at the heating temperature. In addition, a part of the softened toner adheres to a heating member and transfers to a transfer paper to transfer an image. It is necessary to prevent the occurrence of the so-called offset phenomenon, that is, soiling. In order to improve the offset phenomenon, polyolefins such as low molecular weight polyethylene and polypropylene are contained in toner particles as disclosed in JP-A-49-6523 and JP-A-50-27.
No. 546, for example.

JP-A-1-113765 proposes a developer in which wax-containing toner particles and resin fine particles smaller than the toner particles are mixed. In the developer, spherical organic fine particles are preferred.

However, when a developer having such a polyolefin-containing toner is used in an image forming apparatus having a contact charging device, the following problems are likely to occur.

Polyolefin has poor compatibility with the binder resin of the toner particles, and the polyolefin particles having a large dispersion diameter easily become free polyolefin particles at the time of pulverization at the time of producing the toner. Since high free polyolefin particles are transferred from the electrostatic latent image holding member to the contact charging member and the surface resistance increases, poor charging easily occurs.

The free polyolefin particles have a high resistance and are negatively chargeable with respect to iron powder, so that fog due to poor charging is deteriorated with respect to negatively chargeable developers and fluidity with respect to positively chargeable developers. Of the image, and the image whitening phenomenon and the image density unevenness are likely to occur.

On the other hand, in recent years, with the widespread use of image forming apparatuses such as electrophotographic copiers, their uses have been widened in various ways, and requirements for image quality have become strict.
In copying an image such as a general document or book, it is required to reproduce very finely and faithfully without crushing or breaking even fine characters. In particular, when the latent image on the photoreceptor of the image forming apparatus is a line image having a size of 100 μm or less, thin line reproducibility is generally poor, and the sharpness of the line image is not yet sufficient. 2. Description of the Related Art Recently, in an image forming apparatus such as an electrophotographic printer using a digital image signal, a latent image is formed by collecting constant potential dots, and a solid portion, a halftone portion, and a light portion change dot density. It is expressed by things. However, when the toner particles do not adhere to the dots and the toner particles protrude from the dots, the gradation of the toner image corresponding to the dot density ratio of the black portion and the white portion of the digital latent image cannot be obtained. There is a problem. Further, when the resolution is improved by reducing the dot size in order to improve the image quality, the reproducibility of a latent image formed from minute dots becomes more difficult, and the resolution and gradation are poor. Images tend to be poor.

Several developers have been proposed for the purpose of improving image quality.

JP-A-1-112253 and JP-A-2-284158 propose a small-diameter toner having a specific particle size distribution. As the diameter of the toner decreases, it is necessary to uniformly charge the surface of the toner particles. Therefore, in order to achieve both a stable charge amount and excellent fluidity, it is preferable to add a dye or a derivative of a dye, which can obtain a proper charge amount with a small amount, as a charge control agent.

However, as the diameter of the toner becomes smaller, free charge control agent particles are more likely to be generated in the pulverizing step, and the flowability is impaired and the developer is more likely to be contaminated, especially when the member in contact with the photoreceptor is contaminated. Was liable to cause uneven charging.

JP-A-1-113762 proposes a developer in which acrylic resin fine particles are mixed with toner particles having a charge control agent. In the developer, spherical organic fine particles are preferred.

However, when a developer containing such a dye or a derivative of the dye as a charge control agent is used in an image forming apparatus having a contact charging device, the following problems are likely to occur.

Since the dye-based charge control agent is soft and sticky, it is released from the toner particles and transferred to the contact charging member, and the surface resistance increases, so that poor charging or poor transfer is likely to occur.

Since the released charge control agent has a high chargeability, it inhibits the charging of the toner particles and at the same time deteriorates the flowability, and is liable to cause image blanking and image density unevenness.

[0034]

SUMMARY OF THE INVENTION An object of the present invention is to provide a developer for developing an electrostatic latent image, an image forming method, an electrophotographic apparatus, an apparatus unit, and a facsimile apparatus which solve the above-mentioned conventional problems. And

An object of the present invention is to provide a developer for developing an electrostatic image in which toner fusion does not or hardly occur on a photosensitive member.

It is an object of the present invention to provide a developer for developing an electrostatic charge image which does not cause charging unevenness even when a large number of images are formed in an image forming method having a contact charging step.

An object of the present invention is to provide a developer for developing an electrostatic latent image having high fluidity and uniform chargeability.

It is an object of the present invention to provide a developer for developing an electrostatic latent image having good fixing characteristics when fixing with a heating roller and good offset resistance.

The present invention provides a developer for developing an electrostatic latent image, an image forming method, an electrophotographic apparatus, an apparatus unit, and a facsimile apparatus, which have a high image density and do not cause fogging and filming on a photosensitive member. The purpose is to:

The present invention does not contaminate the contact charging member when the developing method of charging the electrostatic latent image holding member using the contact charging member is used. A developer for developing an electrostatic latent image that does not occur,
It is an object to provide an image forming method, an electrophotographic apparatus, an apparatus unit, and a facsimile apparatus.

According to the present invention, there is provided a developer for developing an electrostatic latent image, an image forming method, an image forming method, wherein the toner particles are well charged and the fluidity thereof is kept good and the image whitening phenomenon and the image density unevenness do not occur. An object of the present invention is to provide a photographic apparatus, an apparatus unit, and a facsimile apparatus.

Further, according to the present invention, ultrafine particles are hardly generated, and even when a developing system for charging an electrostatic image carrier using a contact charging member is used, the ultrafine particles are hard to adhere to the contact charging member. Accordingly, a developer for electrostatic image development, an image forming method, an electrophotographic apparatus, and an apparatus unit are less likely to cause poor charging in a low-temperature and low-humidity environment and are less likely to cause toner fusion to the surface of the electrostatic image carrier in a high-temperature and high-humidity environment. And a facsimile machine.

Further, the present invention provides a developer for developing an electrostatic latent image, an image forming method, and a method for producing ultrafine particles which are less likely to be generated and which can obtain a stable image density without inhibiting charging of toner particles.
An object of the present invention is to provide an electrophotographic apparatus, an apparatus unit, and a facsimile apparatus.

Further, according to the present invention, even when a developing method for charging an electrostatic image holder using a contact charging member is used, no poor charging occurs and in the case of a negatively chargeable developer, In the case of a positively chargeable developer, which does not worsen fogging due to poor charging, a developer for developing an electrostatic latent image, which does not cause image whitening phenomenon and image density unevenness due to deterioration of fluidity, image formation It is an object to provide a method, an electrophotographic apparatus, an apparatus unit and a facsimile apparatus.

[0045]

SUMMARY OF THE INVENTION The present invention relates to a developer for developing an electrostatic image, comprising a toner, resin fine particles having a surface area of sphericity of 0.50 to 0.90 and inorganic fine powder. .

Further, according to the present invention, there is provided a charging step in which a charging member to which an external voltage is applied is brought into contact with an electrostatic image holder to perform charging, a step of forming an electrostatic image on the charged electrostatic image holder, Developing the electrostatic image formed on the electrostatic image carrier with a developer to form a developed image, and transferring the developed image on the electrostatic image carrier to a transfer material to form a transfer image The present invention relates to an image forming method having a process, wherein the developer comprises a toner, resin fine particles having a surface area of sphericity of 0.50 to 0.90 and inorganic fine powder.

Further, the present invention provides an electrostatic image carrier; a contact charging member to which an external voltage is applied for charging the electrostatic image carrier while contacting the electrostatic image carrier; Electrostatic image forming means for forming an image; developing means for developing an electrostatic image provided with a developer carrier and a developer container for housing the developer to form a developed image; and An electrophotographic apparatus comprising: a transfer unit for transferring a developed image on the electrostatic image holding member to a transfer material;
The present invention relates to an electrophotographic apparatus having 0 to 0.90 resin fine particles and inorganic fine powder.

Further, in the present invention, a unit is formed by integrally supporting at least the developing means and the electrostatic image holder,
In the device unit as a single unit detachable from the device main body, the developer held in the developing means has toner, resin fine particles having a surface area of sphericity of 0.50 to 0.90, and inorganic fine powder. And a device unit characterized by the following.

Further, according to the present invention, there is provided a facsimile apparatus having an electrophotographic apparatus and a receiving means for receiving image information from a remote terminal, wherein the electrophotographic apparatus comprises: an electrostatic image holder; A contact charging member to which an external voltage is applied to perform charging, an electrostatic image forming means for forming an electrostatic image on the charged electrostatic image carrier, and developing the formed electrostatic image by developing A developing unit for forming an image; and a transfer unit for transferring the developed image to a transfer material. The developer held in the developing unit includes a toner, a surface area sphericity of φ0. 50 ~
The present invention relates to a facsimile machine having 0.90 resin fine particles and inorganic fine powder.

Further, the present invention will be described in detail.

In the present invention, the reason why the resin fine particles are effective in fusing the toner to the electrostatic charge image carrier such as the photosensitive member is considered as follows.

As a cause of the fusion of the toner to the photoreceptor, there is a flaw caused by the surface of the photoreceptor being rubbed by the contact charging member to which the inorganic fine powder is adhered. In order to prevent the occurrence of scratches, it is preferable to remove the free inorganic fine powder at the contact portion between the contact charging member and the photoconductor, and as a result, it is effective in preventing toner fusion to the photoconductor. The resin fine particles having a surface area shape sphericity of 0.50 to 0.90 used in the present invention, as compared with true spheres, as schematically shown in FIG.
Since it has a certain degree of unevenness, it has a function of adsorbing a large amount of inorganic fine powder in a free state on the surface.

The spherical polymer particles obtained by the emulsion polymerization method or the soap-free polymerization method generally have very few irregularities on the surface of the polymer particles as schematically shown in FIG.
The surface area sphericity of the polymer particles is greater than 0.90, and generally the surface area sphericity is about 1.

The surface of resin fine particles obtained by mechanically pulverizing a lump of resin or using a jet stream is formed with a fractured surface having a large number of fine irregularities. , Less than 0.50, and generally the surface area shape sphericity の of the resin fine particles is about 0.3 to
0.4.

In an image forming apparatus having a contact charging member, fine resin particles that have slipped off from the cleaning blade are adsorbed by the contact charging member, and then free inorganic fine powder that slips off from the cleaning blade is present on the surface of the contact charging member. It is considered that the resin fine particles are adsorbed, thereby preventing the photoconductor surface from being damaged. At this time, when the amount of the resin fine particles slipping through the cleaning blade is very large, the amount of the free inorganic fine powder is reduced, and the effect of preventing the toner from being fused to the photoconductor is increased, but the thick layer of the resin fine particles is formed on the contact charging member. Formed and therefore
This is one of the causes of poor charging of the photoconductor. As schematically shown in FIG. 1, the fine resin particles used in the present invention have a certain degree of unevenness on the surface, so that the amount of the fine resin particles slipping through the cleaning blade is more appropriately regulated than that of the true spherical particles. The occurrence of charging failure is suppressed.

The surface area of the fine resin particles has a sphericity ０．９ of 0.9.
When the value is larger than 0, occurrence of charging failure of the photoconductor can be seen when a large number of copies (for example, 10,000 or more) are made. Surface area sphericity is 0.5
When it is smaller than 0, the resin fine particles have many irregularities on the surface, have high hygroscopicity, and the developing property of the developer in a high humidity environment tends to deteriorate. Further, during mixing with the toner particles and during the development process, the convex portion of the resin fine particle surface is easily chipped, and there are many pieces of the resin fine particle in the developer,
It is easy to adversely affect development.

The resin fine particles used in the present invention preferably have a number average particle size of primary particles (hereinafter, also simply referred to as “average particle size”) of 0.03 to 1.0 μm, more preferably 0.05 to 1.0 μm.の も の 0.8 μm is used. 1.0μ
Those having a particle size larger than m have a small specific surface area and are not suitable for adsorbing free inorganic fine powder, and have a small effect of preventing fusion of the photoreceptor. On the other hand, when it is smaller than 0.03 μm, the tribo of the developer becomes too high, and the density tends to decrease due to charge-up.

The resin fine particles have a volume resistivity value of 10
Those having ⁶ to 10 ¹³ Ω · cm are preferably used. 10 ⁶
If the resistance is lower than Ω · cm, the charge amount of the developer tends to decrease, and as a result, the image density tends to decrease. 10 ¹³
When resin fine particles higher than Ω · cm are used, the fluidity of the developer tends to be deteriorated, and an image with a lot of fog tends to be formed.

The fine resin particles preferably have an absolute value of not more than +50 μc / g when the triboelectric charge is positively charged and not more than 200 μc / g when the triboelectric charge is negatively charged. + 30μ
More preferably, it is in the range of c / g to 100 μc / g. If the triboelectric charge of the resin fine particles is higher than +50 μc / g, tribo of the developer tends to be unstable, and fogging tends to occur when a large number of copies are made.

The triboelectric charge of the fine particles of the resin is -200.
If it is larger than μc / g (for example, −300 μc / g), the fluidity is likely to be deteriorated, and shading tends to occur on an image.

The resin fine particles are used in an amount of 0.01 to 1.0 part by weight (preferably 0.03 to 1.0 part by weight) based on 100 parts by weight of the toner.
0.57 parts by weight). An inorganic fine powder such as a hydrophobic silica fine powder is used in an amount of 0.1 to 100 parts by weight of the toner.
It is preferably used in an amount of 1 to 3.0 parts by weight. It is preferable to use more of the inorganic fine powder than the fine resin particles.

When the amount of the fine resin particles is more than 1.0 part by weight, the image density tends to decrease.
When the amount is less than the weight part, it is difficult to obtain an effect on the fusion of the photosensitive member.

When the amount of the fine resin particles used is equal to or larger than the amount of the inorganic fine powder, the flowability of the developer is liable to be deteriorated and fog is liable to occur.

The sphericity of the surface area of the resin fine particles is defined as follows.

[0065]

[Outside 1]

The actual measurement of the BET specific surface area can be performed, for example, by using QUAN
When the specific surface area meter Autosorb 1 manufactured by TACHROME is used, examples of the measuring method include the following.

About 0.3 g of resin fine particles are weighed in a cell,
Deaeration is performed at a temperature of 40 ° C. and a degree of vacuum of 1.0 × 10 ⁻³ mmHg for 1 hour or more. Thereafter, nitrogen gas is adsorbed in a state of being cooled by liquid nitrogen, and a value is obtained by a multipoint method.

The surface area assuming that the fine resin particles are true spheres is, for example, an electron micrograph (× 1000) of the fine resin particles.
From 0), 100 resin fine particle images are randomly selected, their major diameters are measured, and the average major diameter value is defined as the diameter when the resin fine particles are assumed to be true spheres. Based on this diameter, the radius γ of the resin fine particles is determined, and further, the surface area (4πγ ² ) of the resin fine particles is determined. In addition, the volume of resin particles

[0069]

[Outside 2] And the weight of the resin fine particles is determined from the density of the resin fine particles and the volume. From the obtained surface area and the weight, the surface area (m ² / g) assuming that the resin fine particles are spherical is determined.

The tribo value of the resin fine particles used in the present invention is measured by the following method. 0.2 g of resin fine particles left for 12 hours or more in an environment of 23.5 ° C. and 60% RH;
Carrier iron powder having a main particle size of 200 to 300 mesh and not coated with a resin (for example, E
(FV200 / 300) was precisely weighed in the above environment under the above-mentioned environment to obtain about 50 c. c. In a wide-mouth bottle with a polyethylene lid having a capacity of
Shake 5 times for about 50 seconds).

Next, as shown in FIG. 10, about 2.0 g of the mixture is placed in a metal measuring container 32 having a 400-mesh screen 33 at the bottom, and a metal lid 34 is placed. At this time, the weight of the entire measurement container 32 is weighed and is defined as W ₁ (g).
Next, in the suction device 31 (at least the portion in contact with the measurement container 32 is at least an insulator), the pressure of the vacuum gauge 35 that has been suctioned through the suction port 37 and adjusted the air volume control valve 36 is set to 250 mmHg.
And In this state, suction is performed for 5 minutes to remove the resin fine particles by suction. The potential of the electrometer 39 at this time is set to V (volt). Here, 38 is the capacity of the capacitor C
(ΜF). Weigh the entire measuring container after suction and weigh W
₂ (g). The triboelectric charge (μc
/ G) is calculated as follows.

[0072]

[Outside 3]

An example of the measurement of the specific electrical resistance (volume specific resistance) in the present invention will be described. The sample is formed into tablets using the apparatus shown in FIG. First, about 0.3 g of the sample is placed in the tableting chamber. Next, the push rod 42 is inserted into the tablet forming chamber and pressurized by the hydraulic pump 45 at 250 kg / cm ² for 5 minutes to form a pellet-shaped tablet having a diameter of about 13 mm and a height of about 2 to 3 mm.

The tablet obtained here is coated with a conductive agent on the front surface and the back surface, if necessary, for example, HEWLETT.
16008A RESISTIVI manufactured by PAKARD
TYCELL; or YOKOGAWA HEWRET
4329A HIGH RESI made by T PAKARD
The resistance value when a voltage of 1000 V is applied is measured using a STANCE METER in an environment of a temperature of 23.5 ° C. and a humidity of 65% RH, and a specific electric resistance value ρ is obtained by calculation.

[0075]

[Outside 4] (Where S is the cross-sectional area of the sample, l is the height of the sample)

The resin fine particles can be produced by adjusting production conditions by an emulsion polymerization method or a spray drying method. Preferably, it is obtained by copolymerizing components such as styrene, acrylic acid, methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate used in a binder resin for a toner by an emulsion polymerization method. Resin particles having a glass transition point of 80 ° C. or more show a good effect.

The surface may be cross-linked with a cross-linking agent such as divinylbenzene, and the surface may be treated with a metal, metal oxide, pigment, dye, surfactant or the like to adjust the specific electric resistance and triboelectric charge. .

The resin fine particles in the present invention are particularly preferably block or random styrene copolymers containing 51% by weight or more of styrene monomer units.
The styrene-based resin fine particles generally have a similar charge sequence to the styrene-acrylic resin or polyester resin used as the binder resin of the developer, have little mutual charge with the toner particles, and do not easily deteriorate in fluidity. Therefore, a styrene resin is preferable as the binder resin of the toner.

When the styrene monomer unit content in the resin fine particles is less than 51% by weight, the cohesiveness of the developer becomes strong, the fluidity is deteriorated, and image blanking and image density unevenness tend to occur.

In a production method such as an emulsion polymerization method, the value of Δ tends to decrease as the content of the styrene monomer increases in the styrene resin fine particles.

The styrene-based resin fine particles having a φ of 0.50 to 0.90 according to the present invention can be obtained by controlling the monomer composition, the monomer composition ratio and the polymerization conditions.

The inorganic fine powder used in the present invention is BET.
Surface area by nitrogen adsorption measured by the method is 70-300m
Those in the range of ² / g give good results. Toner 1
0.1 to 3.0 parts by weight of inorganic fine powder with respect to 00 parts by weight,
Preferably, 0.2 to 2.0 parts by weight is used.

The inorganic fine powder is preferably subjected to a hydrophobic treatment. In particular, negatively charged hydrophobic silica fine powder is preferable.

The inorganic fine powder used in the present invention preferably has a triboelectric charge of -100 μc / g to −300 μc / g. Tribo charge amount is -100 μc /
If the amount is less than g, the amount of triboelectricity of the developer itself is reduced, and the humidity characteristics are likely to be reduced. If the amount exceeds -300 μc / g, the developer carrier memory is promoted, the inorganic fine powder is easily affected, and the durability is likely to be affected. Those finer than 300 m ² / g have little effect on the addition to the developer, and those coarser than 70 m ² / g have a greater probability of being present as free matter, which may cause uneven distribution of inorganic fine powder and black spots due to aggregates. Cheap.

The tribo value of the inorganic fine powder is measured by the following method. 0.2 g of inorganic fine powder left overnight in an environment of a temperature of 23.5 ° C. and a humidity of 60% RH, and a carrier iron powder not coated with resin and having a main particle size of 200 to 300 mesh (for example, Nippon Iron (EFV200 / 300 manufactured by Kosha Co.)
9.8 g was precisely weighed under the above-mentioned environment, and approximately 50 c. c.
Mix thoroughly (hold in hand and shake up and down about 50 times for about 20 seconds) in a polyethylene jar with a volume of.

Next, the triboelectric charge of the inorganic fine powder is measured in the same manner as the measurement of the triboelectric charge of the resin fine particles described above.

Particularly preferred among the inorganic fine powders used in the present invention are those produced from so-called dry method or fumed silica produced by vapor phase oxidation of a silicon halide compound, dry silica, and water glass. Both so-called wet silicas that can be used can be used. Among them, fewer silanol groups on the inner surface and the silica fine powder, also Na ₂ O, who dry silica without producing residue, such as SO _^2-3 is preferred. In the case of fumed silica, for example, a composite fine powder of silica and another metal oxide can be obtained by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide in the production process. In the present invention, the inorganic fine powder also includes them.

The average particle size of the inorganic fine powder is preferably in the range of 0.001 to 2 μm, particularly preferably 0.002 to 0.2 μm. Good to use.

The inorganic fine powder used in the present invention is preferably hydrophobic.

For the hydrophobizing treatment, conventionally known hydrophobizing agents and methods are used. As the hydrophobizing agent, a silicon compound having an organosiloxane unit such as silicone oil or silicone varnish is preferably used.

The silicone oil used for the treatment of the fine powder used in the present invention is represented by the general formula

[0092]

[Outside 5] [R represents an alkyl group having 1 to 3 carbon atoms, R ′ represents an alkyl group, a halogen-modified alkyl group, a phenyl group, or a silicone oil-modified group such as a modified phenyl;
R '' represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and m and n each represent an integer]. Examples thereof include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. The silicone oil is not limited to the above formula.

The above silicone oil preferably has a viscosity of 50 to 1000 centistokes at a temperature of 25 ° C. If it is less than 50 centistokes, it exerts a part due to the application of heat, and the charging characteristics are likely to deteriorate. If it exceeds 1,000 centistokes, handling becomes difficult due to the processing operation. Known techniques can be used as a method of treating the silicone oil. For example, fine silica powder and silicone oil are mixed using a mixer. The silicone oil is sprayed into the fine silica powder using a sprayer. Alternatively, a method of dissolving a silicone oil in a solvent and then mixing a fine silica powder is used. The processing method is not limited to this.

As the silicone varnish for treating the fine silica powder used in the present invention, known substances can be used.

For example, KR-25 manufactured by Shin-Etsu Silicone Co., Ltd.
1, KP-112 and the like, but are not limited thereto.

As the method of the silicone varnish treatment, the same known technique as the oil treatment can be used. The above treated silica fine powder (hereinafter referred to as treated silica) exerts its effect when it is used in an amount of 0.1 to 1.6 parts by weight with respect to 100 parts by weight of the toner. 3
Excellent stability when added in an amount of from 1.6 to 1.6 parts by weight.
If the amount is less than 0.1 part by weight with respect to 100 parts by weight of the toner, the effect of addition is small. If the amount exceeds 1.6 parts by weight, problems of development and fixing tend to occur, which is not preferable.

A part of the silicon compound having an organosiloxane unit treating the surface of the inorganic fine powder is transferred to the electrostatic image carrier, and has an effect of further facilitating cleaning of the powder such as free polyolefin. .

The hydrophobicity of the inorganic fine powder in the present invention is
The value measured by the following method is used. Of course, other measurement methods are possible with reference to the measurement method of the present invention.

100 ml of ion-exchanged water and 0.1 g of a sample were placed in a 200 ml separatory funnel of a sealed stopper type, and the mixture was shaken at 90 rpm with a shaking machine (Tabler shaker mixer T2C type).
Shake for 10 minutes. After shaking, the mixture was allowed to stand for 10 minutes, and after the inorganic powder layer and the aqueous layer were separated, the lower aqueous layer was separated for 20 minutes.
~ 30ml, put into a 10mm cell, 500nm
The transmittance is measured with reference to the ion-exchanged water of the blank containing no silica fine powder at the wavelength described above, and the value of the transmittance is used as the degree of hydrophobicity of the inorganic fine powder.

The hydrophobic inorganic fine powder in the present invention preferably has a degree of hydrophobicity of 60% or more (more preferably 90% or more). When the degree of hydrophobicity is less than 60%, it is difficult to obtain a high-quality image due to moisture adsorption of the inorganic fine powder under high humidity.

The developer had a surface area shape sphericity ０．９ of 0.90.
0.50 to 0.50, containing resin fine particles having an average particle size of 0.03 to 1.0 μm and a hydrophobic inorganic fine powder (B),
It is preferable that the hydrophobic inorganic fine powder (B) is contained more than the resin fine particles (A).

The toner according to the present invention has a weight average particle size of 3.5 to 20 μm (preferably 3.5 to 14 μm, more preferably 4 to 8 μm), and a number average particle size of 2.8 to 18 μm (preferably). 2.8 to 13 μm, more preferably 3 to 7 μm).

In particular, a toner having a weight average particle diameter (D ₄ ) of _{4 to} 8 μm is preferable because it has excellent fine line reproducibility and resolution.

The particle size distribution of the toner can be measured by various methods, but in the present invention, the measurement was performed using a Coulter counter.

As a measuring device, Coulter Counter T
An interface (manufactured by Nikkaki) that outputs the number distribution and volume distribution using A-II type (manufactured by Coulter) and CX
-1 Connect a personal computer (Canon),
As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. The measuring method is 100 to 100
In 150 ml, 0.1 to 0.5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant, and 2 to 20 mg of a measurement sample (about 3 particles in number) is added.
10,000 to about 300,000). The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and 1 was used as an aperture by the Coulter Counter TAII.
Using a 00μ aperture, 2 to 40 based on the number
The particle size distribution of the μ particles was measured and the values according to the invention were determined therefrom.

When the toner used in the developer of the present invention has a negative triboelectric property, an organic acid such as a metal complex salt of a salicylic acid, a metal complex of an alkylsalicylic acid, a metal complex of a dialkylsalicylic acid, or a metal complex of naphthoic acid is used as a charge controlling agent. It is preferable to contain a metal complex salt; a dye such as a monoazo dye; and a monoazo dye derivative such as a metal complex salt of a monoazo dye.

Examples of the negative charge control agent for the dye compound include an azo metal complex represented by the following general formula [I].

[0108]

[Outside 6] [Wherein, M represents a coordination center metal, and a coordination number of 6
r, Co, Ni, Mn, Fe and the like. Ar is an aryl group, such as a phenyl group or a naphthyl group, which may have a substituent. Examples of the substituent in this case include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group. X, X ', Y and Y' are -O-, -CO-,
—NH— or —NR— (R is an alkyl group having 1 to 4 carbon atoms).

[0109]

[Outside 7] Represents hydrogen, sodium ion, potassium ion, ammonium ion or aliphatic ammonium ion.] Next, specific examples of the complex will be shown.

[0110]

[Outside 8]

[0111]

[Outside 9]

[0112]

[Outside 10]

[0113]

[Outside 11]

[0114]

[Outside 12]

[0115]

[Outside 13]

On the other hand, as the positive charge control agent, for example, a nigrosine dye and its derivative can be used.

The content of the charge control agent is determined according to the binder resin 1 of the toner.
0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, per 100 parts by weight. If the proportion of the charge control agent is too large, the fluidity of the toner deteriorates and fogging tends to occur, while if it is too small, it is difficult to obtain a sufficient charge amount.

As one of the preferable developer for developing an electrostatic image of the present invention, a toner containing a charge controlling agent and having a weight average particle diameter (D ₄ ) of 4 to 8 μm and an average particle diameter smaller than the toner The surface area shape sphericity ０．９ is 0.90 to 0.
The developer for developing an electrostatic charge image does not have a styrene-based organic fine particle of 50 and inorganic fine particles having an average particle diameter smaller than the organic fine particle.

The binder resin of the toner according to the present invention includes:
Styrene such as polystyrene and polyvinyltoluene and its substituted homopolymer; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacryl Acid dimethylaminoethyl copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isobrene copolymer, styrene -Maleic acid copolymerization , Styrene-maleic acid ester copolymer and other styrene-based copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terbel resin, phenol Resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, paraffin wax, carnauba wax, and the like. These can be used alone or as a mixture.

The toner of the present invention preferably contains a binder resin having 15% or more of a component having a molecular weight of 5,000 or less in a molecular weight distribution measured by gel permeation chromatography (GPC).

The content ratio of the binder resin having a molecular weight of 5,000 or less is a numerical value calculated by calculating the area ratio of the component in a chromatogram showing the molecular weight distribution in GPC measurement.
Using the chromatogram showing the molecular weight distribution in the GPC measurement shown in FIG. 9, the area of the entire peak showing the molecular weight distribution was obtained, and further, the area of the region of the component having a molecular weight of 5000 or less shown by the oblique line was obtained. The content ratio of the component having a molecular weight of 5000 or less of the binder resin is calculated based on the group.

When the component having a molecular weight of 5000 or more is less than 15%, a desktop laser beam printer (L
In a relatively low-pressure heat fixing unit such as a small-sized machine represented by BP), the fixing property tends to deteriorate.

Further, the component having a molecular weight of 5,000 or less is 35
% Is preferred.

It is considered that the components having a molecular weight of 5000 or less tend to have a molecular weight dependence of the glass transition point (Tg), and the Tg of the toner measured over a long period of time tends to be lower. Therefore, when the amount of these components exceeds 35%, the composition exhibits a thermal behavior lower than Tg, which is usually measured, and fusion and filming easily occur.

Although this component particularly improves the pulverizability of the toner, if it exceeds 35%, more pulverizability occurs than necessary in the production of a toner having a weight average particle size of 4 to 8 μm. Worsens efficiency.

In addition, the content of the ultrafine powder which cannot be classified is gradually increased as toner replenishment is repeated, and adheres to a toner triboelectric charging member such as a developing sleeve due to electrostatic force. It tends to hinder triboelectrification and cause deterioration in developability such as image density fog.

In the present invention, GP using THF as a solvent
The molecular weight distribution of the chromatogram by C (gel permeation chromatography) is measured under the following conditions.

The column was stabilized in a 40 ° C. heat chamber and the column at this temperature was treated with THF as solvent.
(Tetrahydrofuran) at a flow rate of 1 ml per minute,
About 10 μl of a THF sample solution is injected and measured. When measuring the molecular weight of a sample, the molecular weight distribution of the sample
It is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As the standard polystyrene samples for preparing the calibration curve, for example, manufactured by Tosoh Corporation or molecular weight of Showa Denko KK 10 ^2-1
Used of about 0 ^7, it is appropriate to use at least about 10 standard polystyrene samples. The detector has R
An I (refractive index) detector is used. As the column, a combination of a plurality of commercially available polystyrene gel columns may be used. For example, a Shodex GPC KF manufactured by Showa Denko KK
−801, 802, 803, 804, 805, 806,
807, 800P combination and Tosoh TSK
_{gelG100OH (H XL), G2000H (} H XL),
G3000H (H _XL ), G4000H (H _XL ), G50
00H (H _XL ), G6000H (H _XL ), G7000H
(H _XL ) and TSKguardcolumn.

The sample is prepared as follows. Place the sample in THF, leave it for several hours, shake it
Mix well with HF (until the sample is no longer united) and let sit for an additional 12 hours. At this time, the time of being left in THF is set to be 24 hours or more. After that, the sample passed through a sample processing filter (pore size: 0.45 to 0.5 μm, for example, available from Maishoridisc H-25-5 Tosoh Corporation, Exiclodisc 25CR Germanic Science Japan, etc.) and passed through GPC. Sample. Sample concentration: 0.5 to 5 mg / ml of resin component
It is prepared so that

The developer of the present invention contains 15% by weight of a component having a molecular weight of 5,000 or less in a molecular weight distribution measured by GPC.
A toner containing the binder resin having the above, styrene-based organic fine particles having an average particle size smaller than the toner, and inorganic fine particles having an average particle size smaller than the organic fine particles; Is preferably in the range of 0.90 to 0.50.

The developer of the present invention is preferably a one-component magnetic developer having a magnetic toner containing a magnetic material in toner particles. In this case, the magnetic material also serves as a colorant. The magnetic substance contained in the magnetic toner includes iron oxides such as magnetite, hematite, and ferrite;
Metals such as cobalt and nickel, or metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium And mixtures thereof.

[0132] magnetic material preferably has a BET specific surface area by the nitrogen adsorption method 1-20 m ² / g, especially 2.5~12m ² /
g is good. Further, magnetic powder having a Mohs hardness of 5 to 7 is preferable. The content of the magnetic powder is 10 to 7 with respect to the weight of the toner.
0% by weight is good.

These magnetic materials have an average particle size of 0.1 to 2 μm.
m, preferably 0.1 to 0.5 μm,
The amount to be contained in the toner is 20 to 200 parts by weight, particularly preferably 100 parts by weight of the resin component.
40 to 150 parts by weight per 100 parts by weight is more preferable.

The magnetic material is

[0135]

[Outside 14] The magnetic properties when applied are coercive force (Hc) 20 to

[0136]

[Outside 15] Those having a saturation magnetization (σs) of 50 to 200 emu / g and a residual magnetization (σr) of 2 to 20 emu / g are preferable.

As the colorant that can be used in the toner, any suitable pigment or dye can be used.

For example, pigments include carbon black, alinine black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, red bengala, phthalocyanine blue, and indanthrene blue. These are used in an amount sufficient to maintain the optical density of the fixed image. It is preferable to use 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight of the pigment based on 100 parts by weight of the resin. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight of the dye is used with respect to 100 parts by weight of the resin. preferable.

The toner of the present invention preferably contains wax in the toner particles.

Examples of the wax include polyolefin wax, solid paraffin wax, micro wax, rice wax, amide wax, fatty acid wax, fatty acid metal salt wax, partially saponified fatty acid ester wax, silicone varnish, higher alcohol,
Calsauwax and the like can be mentioned. The content ratio of the wax is 0.1 to 100 parts by weight of the binder resin of the toner.
The amount is preferably 5 to 20 parts by weight, particularly preferably 1 to 12 parts by weight.

When the content ratio of the wax is too large, the amount of free wax increases, and even with the developer containing the styrene-based resin fine particles of the present invention, problems such as poor cleaning, fixing roller contamination, and deterioration in developability cannot be prevented. On the other hand, when the content ratio of the wax is too small, the fixing property and the offset resistance decrease. The wax preferably has a wide molecular weight distribution, and the weight average molecular weight / number average molecular weight (Mw / Mn) is 5
The above (preferably 5 to 10) is preferable from the viewpoint of improving the cleaning property of the OPC photoconductor.

In the present invention, polyolefin wax is particularly preferred, and polypropylene wax and polyethylene wax are particularly preferred. By using such a wax, more excellent fixing performance, cleaning performance and developing performance can be obtained.

The olefin monomers constituting the polyolefin wax include, for example, ethylene, propylene,
Putene-1, pentene-1, hexene-1, heptene-
1, octene-1, nonene-1, decene-1, or isomers having different unsaturated bond positions, furthermore, 3-methyl-1-butene, 3-methyl-2-pentene,
An olefin monomer having a branched chain consisting of an alkyl group such as 3-propyl-5-methyl-2-hexene can be used.

The molecular weight distribution of the wax according to the present invention is measured, for example, as follows. Measurement conditions A. Equipment: Waters Associates GP
C-150C B. Column: Shodex A-80M C.I. Solvent: O-dichlorobenzene (0.1 wt / vol.
% Ionol) 135 ° C 1.0 ml / min Sample preparation Concentration: 0.1 wt / vol% Solubility: Total dissolution at high temperature Filtration: None Injection volume: 400 μl Detector: RI (indicative refractometer) 32 × 50% Molecular weight calibration: Monodisperse polystyrene molecular weight standard

The developer of the present invention comprises a toner containing wax having a weight-average molecular weight / number-average molecular weight (Mw / Mn) of 5 or more, styrene-based organic fine particles having an average particle size smaller than the toner, and styrene. Inorganic fine particles having an average particle diameter smaller than that of the organic fine particles, and the styrene organic fine particles have a surface area shape sphericity ψ of 0.90 to 0.50.
It is good to be in the range.

The developer of the present invention may further contain other additives such as a lubricant such as Teflon or zinc stearate, or a metal oxide such as tin oxide as a conductivity-imparting agent, as long as it does not substantially adversely affect the developer. May be added.

In the production of the toner, a method in which the constituent materials are thoroughly kneaded by a heat kneader such as a hot roll, kneader, extruder, and then pulverized and classified;
A method in which another material is dispersed in a binder resin solution and then obtained by spray drying; a toner which is obtained by mixing a predetermined material with a monomer to constitute the binder resin to form an emulsified suspension and then polymerizing the emulsion. And the like.

The developer of the present invention can be prepared by dry-mixing the toner, organic resin fine particles and inorganic fine powder with a mixer such as a Henschel mixer.

Hereinafter, the contact charging step suitably used in the present invention will be specifically described.

FIG. 3 is a schematic structural view of a specific example of the contact charging device. Reference numeral 1 denotes a photosensitive drum which is a member to be charged as an electrostatic image holder, and an organic photoconductor (OPC) 1b which is a photosensitive layer is formed on an outer peripheral surface of a drum base 1a made of aluminum as a conductive base. It rotates at a predetermined speed in the direction of the arrow. In this specific example, the photosensitive drum 1 has an outer diameter of 30 mmφ. Reference numeral 2 denotes a charging roller, which is a charging member brought into contact with the photosensitive drum 1 at a predetermined pressure, provided with a conductive rubber layer 2b on a metal core 2a, and a surface layer 2c as a release coating on the peripheral surface thereof. Is provided. The conductive rubber layer is 0.5 to 10 mm (preferably 1 to 10 mm).
5 mm). The surface layer in this specific example is a release film, and the provision of the release film is preferable for matching with the developer and the image forming method according to the present invention. However, if the resistance is too large, the photosensitive drum 1 is not charged, and if the resistance is too small, a large voltage is applied to the photosensitive drum 1 and the drum is likely to be damaged and pinholes are generated. It is good to have a moderate resistance. The release film preferably has a volume resistivity of 10 ^{9 to} 10 ¹⁴ Ωm, and the thickness of the release film at this time is preferably 30 μm or less. The lower limit of the thickness of the film is considered to be about 5 μm if the film is free of peeling and burrs. Preferably, the thickness of the release coating is from 10 to 3
0 μm is good.

In this example, the outer diameter of the charging roller 2 is 12
mm, and a conductive rubber layer 2b having a thickness of 3.5 mm
Is an ethylene-propylene-diene terpolymer (EPD)
M) For the surface layer 2c, a nylon resin having a thickness of 10 μm is used. The hardness of the charging roller 2 is 54.5 ° (AS
KER-C). E denotes a power supply unit for applying a voltage to the charging roller 2 to apply a predetermined voltage to the core metal 2 of the charging roller 2.
a (diameter 5 mm). In FIG. 3, E indicates a DC voltage, but it is preferable that the AC voltage is superimposed on the DC voltage as shown in FIG.

The preferred contact charging process conditions in this case are shown below. Contact pressure: 5 to 500 g / cm AC voltage: 0.5 to 5 KVpp AC frequency: 50 to 3000 Hz DC voltage: -200 to -900 V

FIG. 4 is a schematic structural view of a contact charging member showing another embodiment according to the present invention. The same reference numerals are given to the same members as those in the above-described device of FIG. 3, and the description thereof will not be repeated.

The contact charging member 3 of this embodiment is in the form of a blade which is brought into contact with the photosensitive drum 1 in a forward direction at a predetermined pressure. The blade 2 'is connected to a metal supporting member 3a to which a voltage is supplied. A conductive rubber 3b is supported, and a surface layer 3c serving as a releasable coating is provided at a contact portion with the photosensitive drum 1.
Is provided. Nylon having a thickness of 10 μm was used as the surface layer 3c. According to this specific example, the same operation and effect as those of the above-described embodiment can be obtained without any trouble such as adhesion between the blade and the photosensitive drum.

In the above-described specific example, the roller-shaped or blade-shaped charging member is used. However, the present invention is not limited to this, and the present invention can be applied to other shapes.

In this specific example, the charging member is composed of the conductive rubber layer and the release coating, but is not limited to this. For example, a high resistance layer (for example, a hydrin rubber layer with small environmental fluctuation) may be preferably formed between the conductive rubber layer and the surface layer of the release coating to prevent leakage to the photoconductor.

As the release film, PVDF (polyvinylidene fluoride) or PVDC (polyvinylidene chloride) may be used instead of the nylon resin. As the photoconductor, amorphous silicon, selenium, ZnO or the like can be used. When amorphous silicon is used for the photoreceptor, if the softening agent of the conductive rubber layer adheres to the photoreceptor even a little, compared with the case where other materials are used, the image flow becomes worse, so the insulation outside the conductive rubber layer is insulated. The effect of forming the functional coating is great.

The present invention is particularly effective for an image forming apparatus provided with an electrostatic image holder in which the surface of the electrostatic image holder (photosensitive drum) is formed of an organic compound. When the organic compound forms the surface layer, the binder resin contained in the toner and the surface layer easily adhere to each other. Particularly, when the same material is used, toner fusion occurs at the contact point. Because it is easy.

As the surface material of the electrostatic image carrier according to the present invention, silicone resin, vinylidene chloride, ethylene-
PVC, styrene-acrylonitrile, styrene-methyl methacrylate, styrene, polyethylene terephthalate, polycarbonate and the like. The present invention is not limited to these, and other monomers or copolymerization or blending between the exemplified resins can be used.

In the present invention, the diameter of the electrostatic image holder is 50 m.
This is particularly effective for an image forming apparatus of m or less. This is because, in the case of a small-diameter drum, even if the line pressure is the same, the curvature is large, so that the pressure tends to concentrate at the contact portion.

It is considered that the same development is performed on the belt photoreceptor, which is particularly effective for an image forming apparatus having a radius of curvature of 25 mm or less at the transfer portion.

The developer for developing an electrostatic image of the present invention can be preferably used particularly for a heating roller fixing system. The heating roller fixing device generally includes a heating roller, a pressure roller disposed in contact with the heating roller, and a heating source built in the roller. A cleaning roller is disposed in contact with the heating roller as needed. In fixing developer,
The toner image is brought into direct contact with the heating roller by passing the transfer material having the transferred toner image between the heating roller and the pressure roller while maintaining the temperature of the heating roller within a certain range by the heating source. To fix the toner image on the transfer material by heat and pressure. The material of the heating roller is preferably a fluorine-based material or a silicone-based material, and the durability of the heating roller can be remarkably improved by a synergistic effect with the developer of the present invention.

Further, the image forming method and the electrophotographic apparatus of the present invention will be described with reference to a specific example shown in FIG.

The surface of the laminated organic photoconductive photoconductor 501 as an electrostatic image carrier is negatively charged by the above-mentioned contact charger 502 having a voltage application unit 515, and a laser beam is used as a latent image forming unit. A digital latent image is formed by image scanning by exposure 505, and the magnetic blade 5
Negative charging monocomponent magnetic developer 51 in a developing device 509 having a developing sleeve 504 containing a magnet 11 and a magnet.
At 0, the latent image is reverse developed. In the developing section, between the conductive substrate of the photosensitive drum 501 and the developing sleeve 504, an alternating bias, a pulse bias and / or a DC bias are applied by a bias applying means 512. When the transfer paper P is conveyed and reaches the transfer section, the transfer means 503 charges the transfer paper P from the rear surface (the side opposite to the photosensitive drum side), whereby the developed image (toner image) on the surface of the photosensitive drum is transferred. It is electrostatically transferred onto a transfer paper P as a material. The transfer paper P separated from the photosensitive drum 501 is subjected to a fixing process by a heating and pressing roller fixing device 507 to fix a transfer image on the transfer paper P.

The one-component magnetic developer remaining on the photosensitive drum after the transfer step is removed by a cleaning device 508 having a cleaning blade (or a cleaning roller). After the cleaning, the photosensitive drum 501 is neutralized by erase exposure if necessary, and the process starting from the charging process by the charger 502 is repeated again. The erase exposure may be omitted when an AC bias is applied to the contact charger 502.

The electrostatic image holding member (photosensitive drum) has the photosensitive layer and the conductive substrate as described above, and moves in the direction of the arrow.
The developing unit rotates so as to move in the same direction as the surface of the electrostatic image holding member. Inside the non-magnetic cylindrical sleeve 504, a multi-pole permanent magnet (magnet roll) as a magnetic field generating means is arranged so as not to rotate. The one-component insulative magnetic developer 510 in the developing device 509 is applied on a non-magnetic cylindrical surface, and is frictionally generated between the surface of the sleeve 504 and the developer.
The developer is given, for example, a negative triboelectric charge. Further, the thickness of the developer layer is reduced (from 30 μm to 500 μm) by disposing an iron magnetic doctor blade 511 close to the cylindrical surface (interval: 50 μm to 500 μm) and opposed to one magnetic pole position of the multipole permanent magnet. The developer layer is formed so as to be non-contact with the gap between the electrostatic image holding member 501 and the developer carrier 504 in the developing section so as to be non-contact. By adjusting the rotation speed of the developer carrier 504, the surface speed of the sleeve is substantially equal to or close to the speed of the electrostatic image holding surface. The opposed magnetic poles may be formed by using permanent magnets instead of iron as the magnetic doctor blade 511. In the developing section, the developer carrier 504 and the electrostatic latent image carrier 5
An AC bias or a pulse bias may be applied by the biasing means 512 to the surface 01. This AC bias has f of 200 to 4,000 Hz and Vpp of 50.
It suffices if it is 0 to 3,000 V.

When the toner particles are transferred in the developing portion, the toner particles are transferred to the electrostatic image side by an electrostatic force on the surface of the electrostatic image holder and an action of an AC bias or a pulse bias.

Instead of the magnetic doctor blade 511,
The thickness of the developer layer may be regulated by pressing using an elastic blade made of an elastic material such as silicone rubber, and the developer may be applied on the developer carrier.

The cleaning step may be performed simultaneously in the charging step, the developing step or the transfer step.

As the electrophotographic apparatus, a plurality of components such as the electrostatic latent image holding member, the developing means, and the cleaning means are integrally connected as an apparatus unit as shown in FIG. May be configured to be detachable from the apparatus main body. For example, a unit is formed by integrally supporting the contact charging means, the developing means and the cleaning means together with the electrostatic image holder, and as a single unit detachable from the apparatus main body, using a guide means such as a rail of the apparatus main body. It may be configured to be detachable.

When the electrophotographic apparatus of the present invention is used as a facsimile printer, the light image exposure 505 as a latent image forming means is an exposure for printing received data. FIG. 8 is a block diagram showing a specific example of this case.

The controller 611 controls the image reading section 610 and the printer 619. The entire controller 611 is controlled by the CPU 617. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 613. Data received from the partner station is sent to the printer 619 through the receiving circuit 612. Predetermined image data is stored in the image memory. Printer controller 61
Reference numeral 8 controls the printer 619. 614 is a telephone.

The image received from the line 615 (image information from the remote terminal connected via the line) is demodulated by the receiving circuit 612, and then the CPU 617 performs a decoding process of the image information, and the image memory 616 Is stored in The image of at least one page is stored in the memory 616.
, The image of the page is recorded. CP
The U 617 reads out one page of image information from the memory 616 and sends out the decoded one page of image information to the printer controller 618. Printer controller 618
The printer 61 receives the image information of one page from the CPU 618 so as to record the image information of the page.
9 is controlled.

The CPU 617 receives the next page during recording by the printer 619.

[0175]

Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on the embodiments. However, this does not limit the embodiment of the present invention at all. Parts in the examples are parts by weight.

Production of Toner Particles Production Example 1 Styrene-n-butyl methacrylate-divinylbenzene copolymer (copolymer ratio 70: 29: 1, Mw = 28)
100 parts) Magnetic fine powder (BET value 7.5 m ² / g) 100 parts Negative charge control agent (Exemplified complex [I] -3) 0.5 part

The above mixture was melt-kneaded with a twin-screw extruder heated to 140 ° C., and the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill. The powder is subjected to air classification and the weight average particle size (D
₄ ) A magnetically classified powder (magnetic toner 1) (Tg 60 ° C.) of 6.8 μm (number average particle size 5.2 μm) was obtained.

Production Example 2 The procedure of Production Example 1 was repeated except that the exemplified complex [I] -2 was used instead of the exemplified complex [I] -3 as a charge controlling agent. A classified powder (magnetic toner 2) was obtained.

Preparation Example 3 The procedure of Preparation Example 2 was repeated except that the exemplified complex [I] -6 was used instead of the exemplified complex [I] -3 as a charge controlling agent. A classified powder (magnetic toner 3) was obtained.

Production Example 4 A magnetic classified powder (magnetic toner 4) having the same average particle diameter as in Production Example 1 was obtained in the same manner as in Production Example 1 except that no negative charge control agent was used.

Production Example 5 The same operation as in Production Example 1 was carried out except that the amount of the magnetic fine powder was changed to 60 parts, and the magnetic classified powder having the same average particle diameter as that of Production Example 1 having a weight average particle diameter of 12.5 μm (magnetic toner) 5) was obtained.

Examples 1 to 5 and Comparative Examples 1 to 5 Resin fine particles and hydrophobic silica fine powder shown in Tables 1 and 2 below were added to 100 parts by weight of the above magnetic toner, mixed with a Henschel mixer, and subjected to one-component magnetic development. Agent was obtained.

Next, each of these prepared one-component magnetic developers was applied with a DC voltage using an electrophotographic apparatus (a modified LBP-8II made by Canon) shown in FIG. 5 having a contact charging device and a cleaning blade made of polyurethane. (-700
V) and an AC voltage (500 Hz, 200 Vpp) are applied to the contact charging device, and a toner is produced using a magnetic toner having a negative triboelectric charge by a reversal development method continuously at a printing speed of 16 sheets (A4 size) / min. An actual image test for forming an image was performed in a low-temperature and low-humidity environment (15 ° C., 10% RH), and the printout image was evaluated. At the same time, the appearance of the charging member (roller type) surface was observed.

The photoreceptor is formed by forming a photoreceptor layer on the outer peripheral surface of an aluminum drum base with a charge generation layer and a charge transport layer (a charge transport compound dispersed in a polycarbonate resin). An OPC photosensitive member having an abrasion amount of 2.5 × 10 ⁻² cm ³ by a wear tester was used.

As described above, the charging roller 2 has a diameter of 12 m.
m, the core metal has a diameter of 5 mm, and the conductive rubber layer 2b
Has a thickness of about 3.5 mm, the releasable coating formed of methoxymethylated nylon has a thickness of 20 μm, and is pressed against the OPC photoreceptor at a total pressure of 1.2 kg (linear pressure 55 g / cm). did.

In the image forming apparatus, the thickness of the toner layer on the sleeve is set to 130 μm, the distance between the sleeve and the OPC photosensitive member is set to 300 μm, and a DC bias (−500 V) is applied.
An image test was performed while applying an AC bias (1800 Hz, 1600 Vpp) to the developing sleeve.

Table 1 shows the physical properties of the resin fine particles (A), Table 2 shows the physical properties of the silica fine powder (B), and Table 3 shows the composition of the developer and the evaluation results. The charging device used in Example 5 was the blade-type charging device shown in FIG. 2, and Examples 1 to 4 and Comparative Examples 1 to 5 used the roller type charging device shown in FIG.

The uneven charging due to contamination of the charging member was evaluated by using a horizontal line image having a line width of about 100 μ at intervals of about 100 μ.

The dot reproducibility was evaluated by observing the reproducibility of an image obtained by developing a checker pattern having a side of 100 μm or 50 μm on a square as shown in FIG.

[0190]

[Table 1]

[0191]

[Table 2]

[0192]

[Table 3]

Production Example 6 Styrene-n-butyl methacrylate-divinylbenzene copolymer (copolymerization ratio 70: 29: 1, Mw = 28)
100 parts Magnetic fine powder (BET value 7.5 m ² / g) 80 parts Negative charge control agent: 3,5-di-tert-butylsalicylate chromium complex 2 parts Low molecular weight polypropylene (Mw /
Mn = 5.8) 8 parts The above mixture was melt-kneaded with a biaxial extruder at 140 ° C, the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized dry product was finely pulverized with a jet mill to obtain a mixture. The finely pulverized powder was subjected to air classification to obtain a weight average particle diameter (D ₄ ) of 7.8 μm
m (number average particle diameter: 6.1 μm) to obtain a magnetically classified powder (magnetic toner 6) (Tg: 60 ° C.).

Production Example 7 A magnetic classified powder (magnetic toner 7) having the same average particle diameter as in Production Example 6 was obtained in the same manner as in Production Example 6, except that Mw / Mn = 6.5 was used as the low molecular weight polypropylene.

Production Example 8 A blend of low molecular weight polyethylene and low molecular weight polypropylene (Mw / Mn) instead of low molecular weight polypropylene
= 8.2) to obtain a magnetically classified powder (magnetic toner 8) having the same average particle size as that of Production Example 1 except that Production Example 6 was used.

Production Example 9 Production Example 6 except that no low molecular weight polypropylene was used.
A magnetic particle classification powder (magnetic toner 9) having an average particle size similar to that of Production Example 6 was obtained.

Examples 8 to 12 and Comparative Examples 4 to 7 Resin fine particles and hydrophobic silica fine powder shown in Tables 1 and 2 were added to the above magnetic toner and mixed with a Henschel mixer to obtain a developer.

Using each of the obtained developers, images were formed and evaluated in the same manner as in Example 1 or 5.

The results are shown in Table 4.

[0200]

[Table 4]

Production of Toner Particles Production Example 10 100 parts of copolymer I 80 parts of magnetic fine powder (BET value 7.5 m ² / g) Negative charge control agent: 3,5-di-tert-butylsalicylic acid Chromium complex 2 parts

The above mixture was melt-kneaded with a biaxial extruder heated to 140 ° C., and the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill. The powder was subjected to air classification to obtain a magnetically classified powder (magnetic toner 10) (Tg / 60 ° C.) having a weight average particle diameter (D ₄ ) of 7.8 μm (number average particle diameter of 6.1 μm).

Production Examples 11 to 13 The procedure of Production Example 10 was repeated except that the copolymers I to IV were used instead of the copolymer I. A magnetically classified powder having the same average particle size as that of Production Example 10 (toner 11-12) were obtained.

Table 5 shows the composition of the copolymer, the Tg, and the weight fraction of the region having a molecular weight of 5,000 or less in toner GPC measurement after toner formation.

[0205]

[Table 5] St; styrene BA; butyl acrylate BMA; butyl methacrylate 2EHA; 2 ethylhexyl acrylate MB; monobutyl maleate

Examples 13 to 17 and Comparative Examples 5 to 8 Resin fine particles and hydrophobic silica fine powder shown in Tables 1 and 2 were added to the above magnetic toner and mixed with a Henschel mixer to obtain a developer.

Each of the obtained developers was imaged and evaluated in the same manner as in Example 1 or 5. The results are shown in Table 6.

Similarly, in a high temperature and high humidity environment (32.5 ° C., 85
% RH), the printout image was evaluated, and the state of the surface of the photoreceptor was observed.

The unevenness in charging due to contamination of the charging member is about 100
It was represented by a horizontal line image having a line width of about 100 μm at μm intervals.
(Under low-temperature and low-humidity environment) The toner fusion to the photoreceptor surface was evaluated based on the number of white spots in a solid black image. did).

The evaluation criteria are shown below. Fusion of toner on photoreceptor surface…: No fusion at all △: Fusion of 1 to 3 points in A4 solid black △: Fusion of 3 to 10 points in A4 solid black ×: Fusion of A4 solid black Fusion of 10 points or more

The fixing property was measured at normal temperature and normal humidity (23.5 ° C. 60
%), The power is turned on after the evaluation machine has adjusted to the environment, and a 200 μm-wide horizontal line pattern (width 200 μm, interval 200 μm) is printed out immediately after the wait-up (A4).
(Vertical) The first printed image was used for evaluation of fixability. Evaluation of fixability: 100 g of 5 reciprocations of the image with silbon paper
Rubbing with load, image peeling, decrease in reflection density (%)
The average was evaluated.

For the evaluation, a bond paper having a surface smoothness of 10 [sec] or less was used. The evaluation criteria are shown below. Fixing ability…: good (density reduction rate of less than 10%) △: somewhat poor but practical (concentration reduction rate of 10% to 20%)
×) Unusable (concentration reduction rate 20% or more)

[0213]

[Table 6]

Production Example 14 Styrene-n-butyl acrylate copolymer (copolymer weight ratio 8: 2, Mw = 270,000) 100 parts Magnetic fine powder (BET value 8.5 m ² / g) 60 parts Negative charge Property control agent (monoazo dye-based chromium complex) 0.6
Parts low molecular weight polypropylene (Mw = 6,000) 3 parts

The above materials were melt-kneaded in a twin-screw extruder heated to 140 ° C., and the cooled kneaded material was coarsely pulverized by a hammer mill, and the coarsely pulverized material was finely pulverized by a jet mill. The powder is classified by wind force and the volume average particle size is 1
2 μm magnetic classification powder [magnetic toner 14] (Tg 60 ° C.)
I got

Production Example 15 Styrene-2-ethylhexyl acrylate-n-butyl maleate half ester copolymer (copolymerization ratio: 7:
2: 1; Mw = 200,000) 100 parts Magnetic fine powder (BET value 7.5 m ² / g) 60 parts Negative charge control agent (salicylic acid chromium complex) 2 parts Low molecular weight polypropylene (Mw = 6,000) 3 copies

The above materials were used in the same manner as in Production Example 14 to obtain a magnetically classified powder [Toner 15] (Tg 55 ° C.).

Examples 18 to 22 and Comparative Examples 12 to 1
4. One-component magnetic development having a toner in which the resin fine particles shown in Table 7 below and the silica fine powder shown in Table 2 above and the magnetic toner particles are mixed with a Henschel mixer, and the resin fine particles and the silica fine powder are externally added to the toner. Agent was obtained.

Next, each of the prepared one-component magnetic developers was applied to a DC voltage and an AC voltage (500 Hz) using an image forming apparatus (LBP-8II modified by Canon) having a contact charging device shown in FIG. , 2000 Vpp) at a printing speed of 16 sheets (A4) / minute, and a real image test using a magnetic toner having a negative triboelectric charge by a reversal development method was conducted at room temperature and normal humidity (25 ° C.). , 60
% RH), and the printout image was evaluated. At the same time, the appearance of the charging member (roller type) and the surface of the OPC photosensitive drum were observed.

Table 7 below shows the physical properties of the resin fine particles (A), and Table 8 shows the composition of the developer and the evaluation results. Table 7
The “particle size” of the resin fine particles (A) in the above is “number average particle size”
Means

The evaluation criteria are shown below. Fogging ○: almost none △: fogged but practically acceptable ×… impossible not practical OPC photoreceptor fusion ○: no fusion at all ○ △: fusion of 1 to 3 points in A4 solid black △: A4 solid black 3 to 10 points of fusion ×: Fusion of 10 points or more in A4 solid black Charging unevenness ○: No charging unevenness Δ: Slight charging unevenness is observed, but practical use is possible ×: Charging unevenness is clear on the image Appears in Impractical

[0222]

[Table 7]

[0223]

[Table 8]

[0224]

As described above, by combining inorganic fine powders such as hydrophobic silica fine powders with specific resin fine particles, free inorganic fine powders are removed to protect the surface of the photoreceptor. The developer of the present invention can provide a high quality toner image free from toner contamination and fogging.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing an example of the appearance of resin fine particles used in the present invention.

FIG. 2 is a diagram schematically showing the appearance of resin fine particles having a surface area shape sphericity of about 1.

FIG. 3 is a schematic explanatory view of a roller-shaped contact charging device.

FIG. 4 is a schematic explanatory view of a roller-shaped contact charging device having an alternating voltage applying unit.

FIG. 5 is a schematic explanatory view of a blade-shaped contact charging device.

FIG. 6 is a schematic explanatory view of one specific example for carrying out the image forming method of the present invention.

FIG. 7 is a schematic explanatory view of one specific example of the device unit of the present invention.

FIG. 8 is a block diagram illustrating a facsimile apparatus according to the present invention.

FIG. 9 is a diagram showing a chromatogram of GPC.

FIG. 10 is a schematic explanatory view of an apparatus for measuring a triboelectric charge amount of a powder sample.

FIG. 11 is a schematic explanatory view of a molding device for tableting powder.

FIG. 12 is a diagram showing a checker pattern.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 electrostatic image holder 1 a drum substrate 1 b photoreceptor layer 2 charging roller 2 a metal core 2 b conductive rubber layer 2 c release coating E DC voltage

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 3-36180 (32) Priority date March 1, 1991 (1991.3.1) (33) Priority claim country Japan (JP) (72) Inventor Masayoshi Kato 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Hiroshi Yuza 3-30-2, Shimomaruko 3-chome, Ota-ku, Tokyo Canon Inc. (72) Invention Kiyoko Tsuchiya Canon Inc. 3-30-2 Shimomaruko, Ota-ku, Tokyo (56) References JP-A-4-209630 (JP, A) JP-A-4-274444 (JP, A)

Claims (44)

(57) [Claims] 1. A toner having a sphericity of φ0. 5 0
0. A developer for electrostatic image development, comprising 90 resin fine particles and inorganic fine powder. Wherein the average particle diameter of the resin fine particles 0.03 to 1.
0 μm, the inorganic fine powder is a hydrophobic inorganic fine powder,
2. The developer for developing an electrostatic image according to claim 1 , wherein the hydrophobic inorganic fine powder is contained more than the resin fine particles. Wherein the toner contains a charge control agent, and the weight average particle diameter (D ₄₎ is 4 to 8 [mu] m, the resin particles
, Rather than the toner is formed in a small styrenic organic fine average particle size, inorganic fine powder, to claim 1 or 2, wherein an average particle diameter than the resin fine particles is small
The developer for developing an electrostatic image according to the above . Wherein said styrene-based organic fine particles, a volume resistivity 10 ⁶ ~10 ¹³ Ω · cm, claim, wherein an average particle diameter one 且 is 0.03~1.0μm 3
The electrostatic image developer according to. 5. The electrostatic image developer according to claim 1 or 2, characterized in that the silica to which the inorganic fine powder has been treated with a silicon compound having at least organosiloxane units. Wherein said toner is formed of toner particles having a weight average molecular weight / number average molecular weight (Mw / Mn) having a 5 or more waxes, the resin fine particles having an average particle size less styrene than the toner The inorganic fine powder is formed of organic fine particles, and the inorganic fine powder has an average particle diameter smaller than that of the resin fine particles.
The developer according to claim 1 , wherein the developer is formed of a powder . 7. The styrenic organic fine particles, a volume resistivity 10 ⁶ ~10 ¹³ Ω · cm, claim, wherein an average particle diameter one 且 is 0.03~1.0μm 6
The electrostatic image developer according to. 8. The electrostatic image developer according to claim 6 or 7, characterized in that a silica the inorganic fine powder has been treated with a silicon compound having at least organosiloxane units. 9. The developer according to claim 6 , wherein the wax is a polyolefin wax. 10. The toner is in the molecular weight distribution in the GPC measurement, the molecular weight of 5000 or less of components containing a binder resin having 15% or more, the resin fine particles, styrene-based organic average particle diameter than the toner is small It is formed by fine particles, inorganic fine powder, the electrostatic charge image developer according to claim 1, characterized in that it is formed by the inorganic fine powder having an average particle size less than the resin particles. 11. The styrene-based organic fine particles, a volume resistivity of 10 ⁶ ~10 ¹³ Ω · cm, claim, wherein an average particle diameter one 且 is 0.03~1.0μm 1
0. The developer for developing an electrostatic image according to 0. 12. The electrostatic image developer according to claim 10 or 11, characterized in that the silica to which the inorganic fine powder has been treated with a silicon compound having at least organosiloxane units. 13. The charging step of the charging member and the external voltage is applied performs charging by contact with the electrostatic <br/> electrostatic Nizo holder, forming an electrostatic image on the charged electrostatic Nizo holder , the electrostatic load
Forming a developed image by developing the electrostatic Nizo formed on the image carrier on the developer, transfer is transferred to the rolling Utsushizai development <br/> image on the electrostatic Nizo holder An image forming method including a transfer step of forming an image, wherein the developer comprises a toner, a surface area shape sphericity φ0. 5 0 to 0. An image forming method comprising 90 resin fine particles and inorganic fine powder. 14. The toner contains a charge control agent, and
A weight average particle diameter (D ₄ ) of 4 to 8 μm;
Styrene-based organic particles having a smaller average particle size than the toner
Formed of fine particles, the inorganic fine powder is
14. The method according to claim 13, wherein the average particle size is also small.
Image forming method. 15. The toner has a weight-average molecular weight / number-average molecular weight
Having wax having a molecular weight (Mw / Mn) of 5 or more
Particles, the fine resin particles are more average than the toner.
It is formed with styrene-based organic fine particles having a small particle size.
Fine powder is an inorganic material with an average particle size smaller than the resin fine particles.
14. The method according to claim 13, wherein the fine powder is formed.
The image forming method as described in the above. 16. The toner according to claim 16, wherein the toner has a molecular weight
In the amount distribution, components having a molecular weight of 5,000 or less
It contains a binder resin having upper, the resin fine particles, the toner
Formed from styrene-based organic fine particles with a smaller average particle size than
The inorganic fine powder has a smaller average particle size than the resin fine particles.
Claims characterized by being formed of fine inorganic powder
Item 14. The image forming method according to Item 13. 17. The styrene-based organic fine particles have a specific volume.
Resistance value is 10 ⁶ -10 ¹³ Ω · cm and average particle size
Is 0.03 to 1.0 μm.
17. The image forming method according to any one of items 14 to 16. 18. The resin fine particles having an average particle size of 0.03 to
1.0 μm, and the inorganic fine powder is a hydrophobic inorganic fine powder.
And the hydrophobic inorganic fine powder is contained more than the resin fine particles.
The method according to any one of claims 13 to 17, wherein
An image forming method according to any one of the preceding claims. 19. The method according to claim 19, wherein the inorganic fine powder comprises at least
Silica treated with a silicon compound having a siloxane unit
19. The method according to claim 13, wherein
2. The image forming method according to 1., 20. The wax according to claim 1, wherein the wax is a polyolefin wax.
The image forming method according to claim 15, wherein
Law. 21. An electrostatic image holder; a contact charging member to which an external voltage is applied for charging the electrostatic image holder while contacting the electrostatic image holder; and forming an electrostatic image on the charged electrostatic image holder. developing means for developing the electrostatic image which comprises a developer container for containing a developer carrying member and the developer to form a developed image; electrostatic image forming means for and electrostatic charge image rolling <br/> copy means for transferring the developed image to the transfer material held on the holding member; an electrophotographic apparatus which comprises a developing agent, a toner, the surface area shape sphericity φ0.50~
An electrophotographic apparatus comprising 0.90 resin fine particles and inorganic fine powder . 22. The toner contains a charge control agent, and
A weight average particle diameter (D ₄ ) of 4 to 8 μm;
Styrene-based organic particles having a smaller average particle size than the toner
Formed of fine particles, the inorganic fine powder is
22. The method according to claim 21, wherein the average particle size is also small.
Electrophotographic equipment. 23. The toner has a weight average molecular weight / number average molecular weight
Having wax having a molecular weight (Mw / Mn) of 5 or more
Particles, the fine resin particles are more average than the toner.
It is formed with styrene-based organic fine particles having a small particle size.
Fine powder is an inorganic material with an average particle size smaller than the resin fine particles.
22. The method according to claim 21, wherein the fine powder is formed.
An electrophotographic apparatus according to the above. 24. The toner according to claim 1, wherein the toner has a molecular weight
In the amount distribution, components having a molecular weight of 5,000 or less
The binder fine particles, wherein the resin fine particles are
Formed from styrene-based organic fine particles with a smaller average particle size than
The inorganic fine powder has a smaller average particle size than the resin fine particles.
Claims characterized by being formed of fine inorganic powder
Item 22. An electrophotographic apparatus according to Item 21. 25. The styrene-based organic fine particles have a specific volume.
Resistance value is 10 ⁶ -10 ¹³ Ω · cm and average particle size
Is 0.03 to 1.0 μm.
25. The electrophotographic apparatus according to any one of 22 to 24. 26. The resin fine particles having an average particle size of 0.03 to 0.03.
1.0 μm, and the inorganic fine powder is a hydrophobic inorganic fine powder.
And the hydrophobic inorganic fine powder is contained more than the resin fine particles.
26. The method according to claim 21, wherein
An electrophotographic apparatus according to any of the preceding claims. 27. The inorganic fine powder comprising at least an organosi
Silica treated with a silicon compound having a siloxane unit
27. The method according to claim 21, wherein
An electrophotographic apparatus according to claim 1. 28. The method according to claim 28, wherein the wax is a polyolefin wax.
The electrophotographic apparatus according to claim 23, wherein:
Place. 29. to form a unit integrally supports at least the developing means and the electrostatic Nizo holder, the apparatus unit having a single unit detachable to the apparatus main body, the developing being held in the developing means The agent is toner, surface area shape sphericity φ0. 5 0 to 0. An apparatus unit comprising 90 resin fine particles and inorganic fine powder. 30. The toner contains a charge control agent, and
Weight average particle size (D _Four ) 4 to 8 μm;
The particles are styrene-based particles having an average particle diameter smaller than that of the toner.
The inorganic fine powder is formed of fine particles of the resin.
30. The method according to claim 29, wherein the average particle size is small.
Equipment unit. 31. The toner has a weight average molecular weight / number average.
Toner having wax having a molecular weight (Mw / Mn) of 5 or more
And the resin fine particles are more flat than the toner.
It is formed with styrene-based organic fine particles having a small uniform particle size.
The inorganic fine powder has a smaller average particle size than the resin fine particles.
30. It is formed of fine powder.
An apparatus unit according to item 1. 32. The toner has a molecular weight measured by GPC.
In the amount distribution, components having a molecular weight of 5,000 or less
The binder fine particles, wherein the resin fine particles are
Formed from styrene-based organic fine particles with a smaller average particle size than
The inorganic fine powder has a smaller average particle size than the resin fine particles.
Claims characterized by being formed of fine inorganic powder
Item 30. The device unit according to item 29. 33. The styrene-based organic fine particles have a specific volume.
Resistance value is 10 ⁶ -10 ¹³ Ω · cm and average particle size
Is 0.03 to 1.0 μm.
33. The device unit according to any one of 30 to 32. 34. The resin fine particles having an average particle size of from 0.03 to 0.03.
1.0 μm, and the inorganic fine powder is a hydrophobic inorganic fine powder.
And the hydrophobic inorganic fine powder is contained more than the resin fine particles.
34. Any of claims 29 to 33, wherein
An apparatus unit according to any of the preceding claims. 35. The method according to claim 35, wherein the inorganic fine powder comprises at least
Silica treated with a silicon compound having a siloxane unit
The method according to any one of claims 29 to 3418, wherein
An apparatus unit according to any of the preceding claims. 36. The wax is a polyolefin wax.
32. The device unit according to claim 31, wherein
G. 37. In a facsimile apparatus having a receiving means for receiving image information from an electrophotographic apparatus and a remote terminal, the electrophotographic apparatus, an electrostatic Nizo holder, in contact with the electrostatic Nizo holder contact charging member external voltage Ru is applied to perform the charging, for forming an electrostatic charge image on the charged electrostatic image bearing member
Electrostatic image forming means, the formed electrostatic Nizo to be developed
Te, developing means for forming a developed image, and, of developing
It has a transfer means for transferring a transfer material the developed image, the developer that is held in the developing means, the toner, the surface area shape sphericity .phi.0. 5 0 to 0. A facsimile machine comprising 90 resin fine particles and inorganic fine powder. 38. The toner contains a charge control agent, and
Weight average particle size (D _Four ) 4 to 8 μm;
The particles are styrene-based particles having an average particle diameter smaller than that of the toner.
The inorganic fine powder is formed of fine particles of the resin.
38. The method according to claim 37, wherein the average particle diameter is small.
Facsimile machine. 39. The toner has a weight-average molecular weight / number-average molecular weight
Having wax having a molecular weight (Mw / Mn) of 5 or more
Particles, the fine resin particles are more average than the toner.
It is formed with styrene-based organic fine particles having a small particle size.
Fine powder is an inorganic material with an average particle size smaller than the resin fine particles.
38. The method according to claim 37, wherein the fine powder is formed.
A facsimile machine as described. 40. The toner has a molecular weight measured by GPC.
In the amount distribution, components having a molecular weight of 5,000 or less
The binder fine particles, wherein the resin fine particles are
Formed from styrene-based organic fine particles with a smaller average particle size than
The inorganic fine powder has a smaller average particle size than the resin fine particles.
Claims characterized by being formed of fine inorganic powder
Item 38. The facsimile apparatus according to Item 37. 41. The styrene-based organic fine particles have a specific volume.
Resistance value is 10 ⁶ -10 ¹³ Ω · cm and average particle size
Is 0.03 to 1.0 μm.
41. The facsimile apparatus according to any one of 38 to 40. 42. The resin fine particles having an average particle size of 0.03 to
1.0 μm, and the inorganic fine powder is a hydrophobic inorganic fine powder.
And the hydrophobic inorganic fine powder is contained more than the resin fine particles.
42. The method according to claim 37, wherein
A facsimile apparatus according to any of the preceding claims. 43. The inorganic fine powder comprising at least an organosi
Silica treated with a silicon compound having a siloxane unit
43. The method according to claim 37, wherein
A facsimile apparatus according to claim 1. 44. The wax according to claim 44, wherein the wax is a polyolefin wax.
40. The facsimile of claim 39, wherein
Device.