JP2002278132A - Electrophotographic method and device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic method and an electrophotographic device by which a high-quality image is stably outputted even when black toner used much is separated, recovered and carried to a developing device so as to be recycled in a high speed monochrome and high image quality full color electrophotographic device. SOLUTION: In this electrophotographic method in which magnetic toner is used as black toner and non-magnetic toner is used as other color toner, an image is formed by using a photoreceptor having at least a photoconductive layer including at least amorphous silicon as an electrophotographic sensitive body and the non-magnetic toner whose average roundness is >=0.960.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for uniformly charging an object to be charged, that is, a photoreceptor, which is an image bearing member, and writing image information on the charged surface with visible light, line scanning laser light, or the like. The present invention relates to a digital electrophotographic method of performing formation. More specifically, this is an electrophotographic method of using an amorphous silicon (a-Si) photoconductor and developing a plurality of colors on the same photoconductor. It relates to an electrophotographic method.

[0002]

2. Description of the Related Art Electrophotographic apparatuses have been widely used in addition to conventional so-called copying machines for copying originals, as well as computers and printers as output means of word processors, which have been growing in demand in recent years. It is important for such a printer that a color image output is provided in addition to a conventional monochrome image output.

In such an environment, conventionally, a plurality of developing units each containing a developer of a different color are provided, and one or more recording cycles are performed on a photosensitive drum as an image carrier using an electrophotographic method. A multicolor image forming apparatus has been proposed in which a plurality of color toner images are formed on a recording material, and the plurality of color toner images are collectively transferred and fixed on a recording material to obtain a desired multicolor image.

Japanese Patent Application Laid-Open No. 9-6201 describes switching between a path for transporting the collected toner collected by the cleaning means to a developing device and a path for transporting the collected toner to a waste toner container. JP-A-2000-98694 describes that a color image is formed using a magnetic developer and a non-magnetic developer.

[0005] From the viewpoint of resource saving, the cost of waste disposal, and the global environment, reducing the amount of waste toner in the developer is an issue to be improved as an electrophotographic apparatus.

[0006]

For this purpose, recovery and reuse of toner have been studied and put to practical use.
However, it is difficult to eliminate contaminants other than the toner contained in the recovered toner (mainly those generated from paper, paper dust and additives), and this affects the quality of the output image. This is one of the technical issues, and is a factor that makes it difficult to mount it on all electrophotographic devices.

In a case where a toner is collected and reused by an apparatus having a developing device for storing a magnetic toner and a developing device for storing a colored non-magnetic toner, a plurality of types of toners having different colors are mixed on a photoreceptor. In such a situation, the toner cannot be reused unless it is separated and collected, so that it is difficult to reuse the toner.

The present invention has been made from such a viewpoint, and provides a full-color electrophotographic apparatus having high image quality and high durability while reducing running costs. Separation,
An object of the present invention is to provide an electrophotographic method and an electrophotographic apparatus which can be reused to reduce waste toner.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made by the inventors of the present invention to make the following arrangements after the intensive study, thereby solving the problems.

That is, the present invention uses a photoreceptor having a photoconductive layer containing at least amorphous silicon formed on a conductive support, and replaces the latent images formed on the photoreceptor with a plurality of toners containing toners of different colors. The toner image is formed by developing with a developing unit, the formed toner image is transferred from the photoconductor to a transfer material by a transfer unit, and the transfer residual toner on the photoconductor after the toner image is transferred is cleaned by the cleaning unit. Removed from the top, using a magnetic toner as a black toner among the toners of different colors, in an electrophotographic method of outputting a full-color image using a non-magnetic toner for the other color toner, the non-magnetic toner is at least a binder resin and An electrophotographic method, which is a spherical non-magnetic toner containing toner particles containing a colorant and inorganic fine powder and having an average circularity of 0.960 or more.

The present invention is also directed to a photoreceptor having at least a conductive support and a photoconductive layer containing amorphous silicon and formed on the conductive support, a charging means for charging the photoreceptor, and a charging means for charging the photoreceptor. A latent image forming means for forming an electrostatic latent image on a surface, and a black developing device for containing a magnetic toner as a black toner and developing the electrostatic latent image formed on the photoreceptor with the magnetic toner to form a black toner image Means, a color developing means for containing a non-magnetic toner of each color, which is a color toner of a different color, and developing an electrostatic latent image formed on the photoreceptor with each non-magnetic toner to form a toner image of each color; In an image forming apparatus having a transfer unit that transfers a formed toner image from a photoconductor to a transfer material and a cleaning unit that removes transfer residual toner on the photoconductor after transfer, the nonmagnetic toner is at least used. Toner particles containing a binder resin and a colorant, and a fine inorganic powder, an average circularity of 0.96
Provided is an electrophotographic apparatus which is a spherical non-magnetic toner of 0 or more.

Further, according to the present invention, in the a-Si photosensitive member, a surface layer whose surface free energy is in a specific range,
By using a non-magnetic toner having a circularity in a specific range, the toner image on the a-Si-based photoconductor is transferred to a transfer member, and further, when transferred to a transfer material holding the toner image, a high-definition image is formed. Images can be obtained.

In particular, the a-Si-based photoreceptor has a technical difficulty in increasing the electric field for transferring the toner because the dielectric breakdown voltage is sometimes lower than that of the organic photosensitive layer. For this reason, a latent image can be finely developed with a developer in the past, but there was a point to be improved in the image quality when the developed image was transferred to a transfer member and further to a transfer material. These appear as phenomena such as a decrease in image quality during durability and a decrease in density gradation.

In particular, when a magnetic toner is used as a black toner, transfer characteristics with other non-magnetic toners are different, and there has been a technical difficulty in satisfying all of them. The present invention provides means for solving these technical problems and realizing a high-definition image.

Regarding the separation and recovery of toner, a conventional magnet roller is arranged such that the magnetic toner spikes abut on the photoreceptor with an arbitrary nip width and rubs the photoreceptor surface. Although the cleaning was performed by rotation, the present inventors contacted the magnet roller or arranged it with a small gap, and provided toner cleaning means that mainly captures only magnetic toner. The relationship between the amount of toner supplied, the amount of toner captured by the magnet roller, and the amount of toner recoverable from the magnet roller was examined for magnetic and non-magnetic toners. Instead, it has been found that when the supply amount exceeds a certain value, the amount of collected toner tends to rise.

The non-magnetic toner is mainly cleaned by a cleaning blade and collected as waste toner. A very small amount of the non-magnetic toner is captured at the tip of the magnetic toner on the magnet roller. It has been found that most of this minute amount of non-magnetic toner is separated from the magnet roller at the doctor roller portion when a doctor roller described later is used.

Further, when the magnet roller and the photoreceptor are rubbed with each other, the inorganic fine powder on the surface of the toner is peeled off, thereby deteriorating the toner. However, the polymerization toner is less deteriorated than the pulverized toner. Further, it has been found that when the non-magnetic polymerized toner and the magnetic pulverized toner are mixed, the deterioration of the pulverized toner is reduced, probably because the polymerized toner having a high circularity acts as a lubricant.

Although the details are not yet known, when the surface free energy of the photoreceptor becomes 35 to 65 mN / m, the releasability of the toner is improved, and the release of the toner is improved by forming an amorphous carbon-based surface layer containing a large amount of carbon. Properties are further improved, and the toner recovery rate is improved. As a result, the transfer efficiency to the transfer material has been improved, and the capture efficiency of the magnet roller has also been improved, so that the amount of toner entering the cleaning blade has been reduced, the toner has been packed, and has been transported to the waste toner path. The disappearance (cleaner blocking) phenomenon could be prevented. Further, it was found that a high quality image with less fog and toner scattering was obtained, which also had a favorable effect on transferability.

Further, by improving the recovery and separation rate of the magnetic toner, the recovered and reclaimed toner becomes only the magnetic toner, the waste toner becomes almost non-magnetic spherical toner, the transfer of the magnetic toner to the developing device, and the waste toner of the waste toner. The transfer to the container was facilitated, and the effect of reducing clogging in the middle of the route was obtained.

Further, with respect to substances generated from paper such as paper dust, a full-color toner image is formed on an intermediate transfer member, and then transferred to a recording material such as paper, thereby contaminating foreign substances mixed in residual toner. Was almost eliminated.

[0021]

DETAILED DESCRIPTION OF THE INVENTION The present invention has been made based on the above findings and has the following features. That is, the electrophotographic method of the present invention uses a photoreceptor having a photoconductive layer containing at least amorphous silicon formed on a conductive support, and forms a plurality of latent images formed on the photoreceptor containing toners of different colors. To form a toner image,
The formed toner image is transferred from the photoconductor to the transfer material by the transfer unit, and the transfer residual toner on the photoconductor after the transfer of the toner image is removed from the photoconductor by the cleaning unit. In an electrophotographic method of outputting a full-color image using a magnetic toner as a toner and a non-magnetic toner as another color toner, the non-magnetic toner includes toner particles containing at least a binder resin and a colorant, and inorganic fine powder. And the average circularity is 0.960
It is a spherical non-magnetic toner as described above.

In the electrophotographic method of the present invention, in the above-described electrophotographic method, it is more preferable that the magnetic toner is separated and collected from the transfer residual toner, and the collected magnetic toner is transported to a developing unit and reused for development.

More specifically, a photoreceptor having a photoconductive layer containing at least amorphous silicon on a conductive support is used, and a latent image formed on the photoreceptor is converted into a plurality of toners containing toners of different colors. The toner image is formed by developing with a developing unit, the formed toner image is transferred from the photoconductor to a transfer material by a transfer unit, and the transfer residual toner on the photoconductor after the toner image is transferred is cleaned by the cleaning unit. In the electrophotographic method of removing a toner from above and using a magnetic toner as a toner of one color among toners of different colors and outputting a full-color image using a non-magnetic toner as a toner of another color, the non-magnetic toner includes at least a binder resin. And a toner particle containing a colorant and an inorganic fine powder, a spherical non-magnetic toner having an average circularity of 0.960 or more,
It is preferable that the magnetic toner is separated and collected from the transfer residual toner, and the collected magnetic toner is transported to a developing unit and reused for development.

The electrophotographic method of the present invention can be realized by the electrophotographic apparatus of the present invention. Hereinafter, the electrophotographic apparatus of the present invention will be described in more detail.

The electrophotographic apparatus of the present invention comprises a conductive support,
And a photoconductor having at least a photoconductive layer formed on a conductive support and containing amorphous silicon, a charging unit for charging the photoconductor, and a latent image forming unit for forming an electrostatic latent image on a charged surface of the photoconductor And a black developing means for containing a magnetic toner which is a black toner and developing the electrostatic latent image formed on the photoreceptor with the magnetic toner to form a black toner image, and a non-magnetic non-magnetic color toner of a different color. Color developing means for storing toner and developing the electrostatic latent image formed on the photoconductor with each non-magnetic toner to form a toner image of each color, and transferring the formed toner image from the photoconductor to a transfer material The non-magnetic toner is a toner particle containing at least a binder resin and a colorant. , And a inorganic fine powder, the average circularity is characterized by a spherical non-magnetic toner is 0.960 or more.

The electrophotographic apparatus of the present invention is preferably the electrophotographic apparatus described above, further comprising a separating and collecting means for separating and collecting the magnetic toner from the transfer residual toner and conveying the collected magnetic toner to the black developing means. Hereinafter, the configuration of the present invention will be described. The toner and the photoconductor will be described last.

The charging means is not particularly limited as long as it charges the photosensitive member. Such charging means include:
Various charging means such as conventionally known corona discharge charging means and contact charging means can be used.

The latent image forming means is not particularly limited as long as it can form an electrostatic latent image on a charged photosensitive member. As such a latent image forming means, various kinds of latent image forming means such as a conventionally known laser generator and LED can be used.

The developing means is not particularly limited as long as it corresponds to a plurality of color toners used in the present invention and accommodates and develops each toner. In the present invention, a magnetic toner and a non-magnetic toner are used, but in the present invention, a developing unit having a structure suitable for each toner is used depending on the type of the toner to be used. As such a developing means, a conventionally known developing means can be used.

The black toner developing means (black developing means) is preferably a means utilizing a magnetic one-component developing method. When the magnetic one-component developing method is used, the scattering of toner can be reduced and the structure of the developing device can be simplified. Therefore, when a plurality of developing devices are arranged as in the present invention, a space-saving design can be realized.

The non-magnetic toner developing means (color developing means) is preferably a means utilizing a two-component developing method. By developing the non-magnetic toner by the two-component developing method, it is possible to design a developer suitable for the high durability of the amorphous silicon photoconductor used in the present invention. Further, by adopting such a configuration, it becomes possible to separate black toner and color toner described later by magnetic force.

Further, it is preferable that the developing means used in the present invention has a toner hopper for storing replenishment toner. It is more preferable that the toner hopper is provided with a stirring member such as a screw for stirring the toner inside as necessary. The toner used in the present invention will be described later in detail.

The transfer means is not particularly limited as long as it transfers the toner image on the photosensitive member to a transfer material. As such a transfer unit, various transfer units conventionally known can be used. In the present invention, plain paper or OHP
For example, a recording material on which a permanent image is to be formed may be used as a transfer material, and a toner image may be directly transferred from a photoreceptor to a recording material. It is preferable for preventing the mixing of paper powder and the like.

The intermediate transfer member receives a transfer of a toner image on a photosensitive member, and transfers the transferred toner image to a secondary transfer member such as the recording material. The intermediate transfer member is not particularly limited as long as it has a function, and various conventionally known intermediate transfer members can be used. Such an intermediate transfer member may be, for example, an endless transfer belt (see FIG. 1) or a drum-shaped transfer drum (see FIG. 8). Further, as for the material and the manufacturing method of the intermediate transfer member, various materials and techniques conventionally known can be used.

The intermediate transfer member is preferably provided with a cleaner for removing residual toner remaining on the intermediate transfer member and powdery contaminants such as paper powder adhering from the recording material from the intermediate transfer member. . As such a cleaner,
Examples include those having a cleaning member such as a blade, a roller, and a brush.

The cleaning means may be any as long as it removes transfer residual toner on the photoreceptor, and various conventionally known cleaning means can be used. As such a cleaning unit, a configuration having a cleaning container for storing the transfer residual toner and a cleaning member for removing the transfer residual toner on the photoconductor and guiding the toner to the cleaning container can be exemplified.

In the cleaning container, it is preferable to provide a recovery path and a waste path, or a transfer residual toner guide path for guiding the stored transfer residual toner to the separation and recovery means, according to the separation and recovery means described later. As the cleaning member, various conventionally known cleaning members such as a blade, a roller, and a brush can be used alone or in combination of two or more.

The separating and collecting means is means for separating magnetic toner and non-magnetic toner from transfer residual toner and collecting magnetic toner. Regarding the separation of the magnetic toner, it is possible to separate the magnetic toner based on the specific gravity of the magnetic toner, the magnetic force of the magnetic toner, and the like. preferable.

The separating and collecting means includes a magnet member for capturing magnetic toner in the transfer residual toner, a non-magnetic toner regulating member for regulating non-magnetic toner on the magnet member and removing it from the magnet member, A disposal path through which the non-magnetic toner removed from the magnet member is guided, a magnetic toner regulating member that regulates the magnetic toner on the magnet member and removes it from the magnet member, and a magnetic toner removed from the magnet member And a recovery route through which the information is guided.

The magnet member is not particularly limited as long as it generates a magnetic force capable of catching the magnetic toner in the transfer residual toner, and may be a general magnet or an electromagnet capable of arbitrarily generating a magnetic force. Can be used. The shape and the like of the magnet member are not particularly limited, but are preferably roller-shaped magnet rollers from the viewpoint of separation efficiency and separation processing speed.

In the case where the magnet member is a magnet roller, by adopting a configuration in which the separation and recovery means is built in the cleaning means, the configuration can be such that the magnet roller also serves as the cleaning member, thereby improving the cleaning efficiency and the cleaning member. , And an improvement in the separation and recovery efficiency of the magnetic toner can be expected. More specifically, a configuration in which a magnet roller is disposed closer to the surface of the photoreceptor on the transfer unit side than the cleaning member can be cited. With such a configuration, the magnetic toner in the transfer residual toner can be used. Are easily captured by the magnet roller, and improvement in separation and collection efficiency can be expected.

The non-magnetic toner regulating member preferably removes the non-magnetic toner preferentially from the toner captured on the magnet member. The magnetic toner has only one color, while the non-magnetic toner has one or more colors (usually three colors). Since the ratio of the non-magnetic toner contained in the transfer residual toner is large, the non-magnetic toner regulating member is formed of a magnetic material. Even if the gap is relatively large, it is possible to remove the non-magnetic toner preferentially.

As the nonmagnetic toner regulating member, various conventionally known regulating members such as a blade, a roller and a brush can be used alone or in combination of two or more. When a plurality of non-magnetic toner regulating members are used, it is more preferable to gradually reduce the gap between the non-magnetic toner regulating member and the magnet member in order to increase the efficiency of separating the non-magnetic toner.

It is preferable that the disposal path is opened at a position where the non-magnetic toner removed by the non-magnetic toner regulating member is guided. If necessary, the opening of the waste path may be provided with an inclination, or a guide member such as a guide blade may be provided as appropriate so that the non-magnetic toner is guided to the waste path.

It is preferable that the magnetic toner regulating member preferentially removes the magnetic toner from the toner captured on the magnet member. As such a configuration, a configuration in which the magnetic toner restricting member is disposed so as to remove the magnetic toner after the removal of the nonmagnetic toner by the nonmagnetic toner restricting member can be cited.

As the magnetic toner regulating member, similarly to the non-magnetic toner regulating member, various conventionally known regulating members such as a blade, a roller, and a brush are used alone or in combination of two or more. be able to. Further, it is preferable to further reduce the gap between the magnetic toner regulating member and the magnet member in order to further increase the separation and recovery efficiency of the magnetic toner.

Preferably, the collection path is open at a position where the magnetic toner removed by the magnetic toner regulating member is guided. Further, similarly to the disposal path, if necessary, the opening of the recovery path may be provided with a slope, or a guide member such as a guide blade may be appropriately provided so that the magnetic toner is guided to the recovery path.

Further, the electrophotographic apparatus of the present invention is provided with a document ratio calculating means for calculating a document ratio of the magnetic toner in the image, and the separation / recovery means is provided in accordance with the calculation result of the document ratio calculating means. It is preferable to provide a recovery path opening / closing valve that freely opens and closes the recovery path from the viewpoint of further improving the recovery rate of the magnetic toner.

Here, the document ratio refers to the ratio of the image to be formed by the magnetic toner image.
The development ratio can be calculated by the ratio of the latent image to be developed by the magnetic toner to the latent image to be developed by the magnetic toner and all non-magnetic toners when the latent image is formed by the latent image forming means. Various techniques known in the art can be used for calculating the document ratio. The relationship between the document ratio and the collection ratio will be described in detail later. However, when the document ratio of the magnetic toner is 1% or more (more preferably, 2% or more), the collection path opening / closing valve is opened and the magnetic toner Preferably, recovery is performed.

The recovery path opening / closing valve is not particularly limited as long as it allows or blocks the intrusion of toner into the recovery path. For example, a butterfly valve provided at the opening of the recovery path so as to be openable and closable, and a waste path Although a switching valve such as a three-way cock for switching between the collecting path and the collecting path can be exemplified, the switching valve is preferably provided in an opening of the collecting path.

The toner conveying means is not particularly limited as long as it conveys the separated and collected magnetic toner to the toner hopper of the above-mentioned black developing means. Technology is available. As such a toner conveying means, for example, a conveying path communicating the collection path and the black developing means, and a conveying member such as a screw conveyor provided in the conveying path and conveying the toner toward the black developing means are used. The configuration can be exemplified.

Further, in addition to the above-described means, the electrophotographic apparatus of the present invention further includes a fixing means for fixing a toner image on a recording material, and a pre-exposure means for erasing a charge history of a photosensitive member after cleaning. And the like.

According to such an electrophotographic apparatus of the present invention, in an electrophotographic method for outputting a full-color image using a black magnetic toner and a colored non-magnetic toner, at least amorphous silicon is applied to the electrophotographic photosensitive member. The adoption of a photoconductor having a photoconductive layer containing a photoconductive layer and a surface layer of which at least the outermost surface is made of an amorphous material containing a carbon element as a main constituent element improves the recovery rate, and the non-magnetic toner for the color toner has an average circular shape. The toner having a degree of circularity of 0.960, preferably 0.970 or more is used, and the toner having a circularity of 0.900 or more and less than 0.970 is 80% or more. Using the magnet roller of the cleaning means without adding a separating means, only the magnetic toner is separated and collected, and supplied to the developing means for black to be developed. Be reused is particularly possible preferably to.

In addition, a magnet roller is arranged in the cleaning means, and a toner introduction port is arranged so that non-magnetic toner falling from the magnet roller is guided to a disposal path, and toner collected from the magnet roller is guided to a reuse path. By doing so, the magnetic toner can be reused without adding a complicated separation and collection function.

Further, the supply amount of the magnetic toner is calculated from the original document ratio of the image, and the configuration is switched to the reuse route only when the supply amount is equal to or more than a certain value, so that components other than the magnetic toner are mixed in the reuse route. By reducing the amount, it is possible to prevent deterioration in the quality of the reused toner.

Hereinafter, as an example of the electrophotographic apparatus of the present invention, an embodiment of the cleaning means and the separation / collection means will be described. In the present embodiment, an embodiment is shown in which the separation and recovery unit is incorporated in the cleaning unit, but the present invention is not limited to this embodiment.

FIG. 9 is a schematic diagram of a cleaning device relating to the cleaning means and the separation and recovery means used in the present invention. The cleaning device includes a cleaning blade (701), a cleaning blade holder (706) that holds the cleaning blade (701), and a control unit that includes a spring and the like that controls the contact pressure of the cleaning blade (701) with the photosensitive member. (702), a toner pool (703), a magnet roller (704), a doctor roller (705-1) for regulating excess developer and the like on the magnet roller (704), a regulating blade (705-2), Further, a transport system (not shown) for transporting and discharging the cleaned toner, a scooping material for preventing so-called "drips", etc., in which transfer residual developer removed by the cleaning blade (701) falls down. .

Since the non-magnetic toner is hardly captured by the magnet roller, most of the non-magnetic toner is removed by the cleaning blade, and is discarded by the transport system (707).
It is led to. The non-magnetic toner captured by the magnet roller (704) is removed from the magnet roller (704) by the collection blade (705-3) and the doctor roller (705-1), and is guided to the disposal path (707). It has become.

The magnetic toner is supplied to the regulating blade (705-
It is removed from the magnet roller (704) in 2) and introduced into the collection path (708). A recovery path opening / closing valve (709) is provided at the opening of the recovery path (708).

[Recovery Blade] Recovery blade (705-
3) The magnet roller (704) is smaller than the regulating blade (705-2) arranged to control the amount of magnetic toner on the magnet roller (704).
The gap is widened. In addition, the recovery blade (705-3) is provided to guide the naturally separated non-magnetic toner to the disposal path because the non-magnetic toner is easily separated from the magnet roller (704).

[Doctor Roller] The doctor roller (70)
5-1) is arranged to control the amount of magnetic toner on the magnet roller (704). The amount of the magnetic toner is controlled by the gap between the doctor roller and the magnet roller and the difference in rotational peripheral speed. Here, the non-magnetic toner is also transferred to the magnet roller (704).
Separate from

[Regulatory Blade] The regulating blade (705-
2) is arranged with the smallest gap in order to finally control the amount of magnetic toner on the magnet roller (704). This regulating blade (70
It is configured to collect the magnetic toner in 5-2).

A collection blade (705-3) for regulating the magnet roller (704), a doctor roller (70)
5-1) The arrangement of the regulating blade (705-2), particularly the gap with the magnet roller (704), is determined by conducting various studies in order to affect the recovery efficiency of the magnetic toner and the mixing ratio of the non-magnetic toner. It is desirable to do.

It is preferable that the driving speed and the driving direction of the magnet roller (704) are appropriately adjusted in accordance with the use conditions and operating conditions of the electrophotographic apparatus to be used.

Hereinafter, the toner and the photoreceptor used in the present invention will be described in more detail. First, the toner used in the present invention will be described.

[Toner] In the present invention, in an electrophotographic method for forming a full-color image, among toners of different colors, a magnetic toner is used only for black and a non-magnetic toner is used for toners of other colors.

The production method of the toner used in the present invention is not particularly limited, but it is preferable to select an appropriate production method according to the required circularity. For example, the toner used in the present invention can be produced by a pulverization method, but the toner particles obtained by this pulverization method are generally irregular in shape, and the average circularity is 0.970 or more. Must be separated mechanically or thermally or by some special treatment. For this reason, from the viewpoint of production volume and cost, it is preferable to manufacture the toner by a suspension polymerization method in order to obtain a product having an average circularity of 0.970 or more. Hereinafter, the pulverization method and the suspension polymerization method of the toner production method will be described.

1) Suspension Polymerization Method In the method for producing a polymerized toner for producing a magnetic or non-magnetic toner related to the electrophotographic method and the electrophotographic apparatus of the present invention, a release agent and a plasticizer are generally contained in a polymerizable monomer. A charge controlling agent, a cross-linking agent, an optional component such as a coloring agent necessary for the toner, specifically, if necessary, a magnetic substance and other additives, for example, in order to reduce the viscosity of a polymer formed by a polymerization reaction. An organic solvent to be added, a polymer, a dispersant, etc. are appropriately added, and a monomer system uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser is used as a dispersion stabilizer. In an aqueous medium containing At this time, the particle size of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to quickly obtain the desired toner particle size. As the timing of the addition of the polymerization initiator, these additives may be added simultaneously with the addition of other additives in the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. . Immediately after granulation and before initiating the polymerization reaction, a polymerization initiator dissolved in a polymerizable monomer or a solvent may be added.

In the production of the polymerized toner relating to the electrophotographic method and the electrophotographic apparatus of the present invention, known surfactants and organic / inorganic dispersants can be used as dispersion stabilizers. Since it is difficult to generate a superfine powder and the dispersion stability is obtained due to its steric hindrance, the stability is not easily degraded even when the reaction temperature is changed, the washing is easy, and the toner is hardly adversely affected.

In the polymerization step, the polymerization temperature is 40
The polymerization is carried out at a temperature of at least 50 ° C., generally from 50 to 90 ° C. When the polymerization is carried out in this temperature range, the release agent and waxes to be sealed inside are precipitated by phase separation, and the encapsulation becomes more complete. In order to consume the remaining polymerizable monomer, the reaction temperature should be 90 to 15 at the end of the polymerization reaction.
It is possible to increase to 0 ° C.

Further, the toner according to the present invention can be prepared by a dispersion polymerization method in which a toner is directly formed using an aqueous organic solvent which is soluble in a monomer and in which a polymer obtained is insoluble, in the presence of a water-soluble polar polymerization initiator. Production is also possible by a method of producing a toner using an emulsion polymerization method typified by a soap-free polymerization method of directly polymerizing to produce a toner, and a method of associating and aggregating polymer particles and the like obtained by emulsion polymerization. .

After completion of the polymerization, the polymerized toner particles are filtered, washed and dried by a known method, mixed with an inorganic fine powder and adhered to the surface to obtain a toner.
In addition, it is also a desirable embodiment of the present invention to insert a classifying step into the manufacturing process and cut coarse or fine powder.

The toner obtained by this suspension polymerization method (hereinafter also referred to as “polymerized toner”) has an average circularity of 0.960, preferably 0.970 or more, since the individual toner particles are substantially spherical in shape. It is preferable to obtain a non-magnetic toner satisfying the following.

2) Pulverizing Method When the magnetic or non-magnetic toner according to the present invention is produced by a pulverizing method, a known method is used.
Binder resin, magnetic material as required, release agent, charge control agent,
In some cases, components necessary as a toner such as a colorant and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then melt-kneaded using a heat kneader such as a heating roll, a kneader, or an extruder. Disperse or dissolve other toner materials such as magnetic material in the resin melted with each other, cool and solidify, pulverize, classify,
The toner particles can be obtained by performing a surface treatment as necessary. Either the classification or the surface treatment may be performed first. In the classification step, it is preferable to use a multi-divider classifier in terms of production efficiency.

The pulverizing step can be performed by a method using a known pulverizer such as a mechanical impact type or a jet type.
In order to obtain a toner having a specific degree of circularity according to the present invention, it is preferable to further apply heat to pulverize or supplementally apply a mechanical impact. Also,
A hot-water bath method in which finely pulverized (classified as necessary) toner particles are dispersed in hot water, a method in which the toner particles pass through a hot air flow, or the like may be used.

Means for applying a mechanical impact force include, for example, a method using a mechanical impact pulverizer such as a Kryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Kogyo, a mechano-fusion system manufactured by Hosokawa Micron Corp. Like a device such as a hybridization system manufactured by Nara Machinery Co., Ltd., the toner is pressed against the inside of the casing by centrifugal force by a high-speed rotating blade, and a mechanical impact force is applied to the toner by a force such as a compressive force or a frictional force. No.

In the case where the mechanical impact method is used, the processing temperature is set to a temperature near the glass transition point Tg of the toner (Tg ±
Thermomechanical impact of applying 10 ° C.) is preferable from the viewpoints of prevention of aggregation and productivity. More preferably, the transfer is performed at a temperature in the range of the glass transition point Tg ± 5 ° C. of the toner, which is particularly effective for improving the transfer efficiency.

On the other hand, the circularity is 0.900 or more and 0.970
For the magnetic toner used in the present invention in which the ratio of the number of toners less than 80% is more than 80%, a toner obtained by a pulverization method is suitable, and is also preferable from the viewpoint of cost.

The black toner used in the present invention is a magnetic toner. The magnetic toner contains at least toner particles containing a binder resin and a magnetic substance, and inorganic fine powder.
The ratio of the number of toners having a circularity of 0.900 or more and less than 0.970 is preferably 80% or more.

The circularity and the number ratio of the magnetic toner are defined. If the circularity of the magnetic toner is smaller than the above range, the density of the developed toner tends to become coarse, and the toner image is fixed. Occasionally, the image quality such as the trailing phenomenon on the non-image portion may be degraded. If it is larger than the above range, the separation rate from the non-magnetic toner tends to decrease, which is not preferable. Accordingly, if the number ratio of the toner within the above-mentioned circularity range is smaller than 80%, the above-described problems may occur, which is not preferable.

As described above, the circularity of the magnetic toner can be adjusted by the method of producing the toner particles.
In addition, it can be adjusted by spheroidizing toner particles having a low circularity, deforming toner particles having a high circularity, mixing toner particles having different circularities, and the like. As a method for producing the toner particles, various conventionally known production methods such as a pulverization method, an emulsion polymerization method, and a suspension polymerization method can be used. Various conventionally known techniques for performing mechanical or thermal treatment can be used for deforming and spheroidizing the toner particles.

As the binder resin, various binder resins known in the art are used. Preferred binder resins include
Examples thereof include a styrene-based resin and a copolymer of a styrene-based compound and an acrylic acid-based compound.

As the magnetic material, various known magnetic materials are used. In the case where toner particles are produced by a polymerization method, for example, it is preferable to use a magnetic material that has been subjected to a hydrophobic treatment with silicone oil, a coupling agent, or the like.

The inorganic fine powder is used for the purpose of improving the fluidity of the toner and controlling the charging property, but the action is not particularly limited, and the type and the like may be appropriately selected according to the purpose. Can be. Suitable inorganic fine powders include nonmagnetic inorganic compounds such as silica, titania, and alumina, and double oxides thereof.
In addition, as the inorganic fine powder, similarly to the magnetic substance, it is preferable to use those subjected to a hydrophobic treatment.

The magnetic toner used in the present invention includes, in addition to these components, other resins such as a polyester resin,
Waxes, charge control agents, coloring agents, etc. In the case of manufacturing by a polymerization method, monomers (for example, styrene compounds and acrylic acid compounds) constituting a binder resin, and if necessary, a polymerization initiator and a crosslinking agent Various conventionally known components such as an agent, a surfactant, and a dispersion stabilizer such as a hardly soluble metal inorganic salt can be used as needed.

In the magnetic toner used in the present invention,
The above-described magnetic material can also serve as a black colorant, and it is not necessary to include a colorant in the toner particles of the black toner, but a colorant such as a dye and a pigment is blended in the toner particles of the black toner. Is also good.

The non-magnetic toner used in the present invention contains toner particles containing at least a binder resin and a colorant, and inorganic fine powder, and has an average circularity of 0.960 to 1.0.
00, preferably 0.970 to 0.995.

If the average circularity of the non-magnetic toner is smaller than the above range, the transferability of the polymerized toner may be reduced, and the separation rate from the magnetic toner may be reduced, which is not preferable. Further, the average circularity of the non-magnetic toner is 0.
If it is larger than 995, cleaning may be difficult, and therefore it is more preferably 0.995 or less.

As the binder resin used for the non-magnetic toner, the same binder resin as the magnetic toner can be used. The binder resin of the non-magnetic toner and the binder resin of the magnetic toner may be resins having the same composition or resins having different compositions.

The colorant used in the non-magnetic toner is not particularly limited as long as it is non-magnetic and is a color required for forming a full-color image, unlike the color of the magnetic toner. For example, the types of colors of the non-magnetic toner include yellow, magenta, cyan, and black, and the non-magnetic toner includes various conventionally known colorings such as dyes and pigments of these colors. Agents can be used.

The non-magnetic toner may contain, in addition to the binder resin and the colorant, various other components similar to the above-described magnetic toner, except for the magnetic substance.

The magnetic toner and the non-magnetic toner used in the present invention may be a one-component toner or a two-component toner, but the magnetic toner is preferably a one-component toner. . The non-magnetic toner is preferably a two-component toner. When a two-component toner is used, a carrier for carrying and transporting the toner may be added in addition to the toner particles and the inorganic fine powder. As the carrier, a carrier such as a conventionally known magnetic carrier can be used. A suitable form of the carrier can be selected according to physical properties such as the particle diameter and charging characteristics of the toner, the surface condition of the developing sleeve in the developing means, and the like.

The circularity in the present invention is defined as a value obtained by dividing the perimeter of a circle having the same projected area as the particle image by the perimeter of the projected image of the particle. In addition, the average circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles, and is an index indicating the degree of unevenness of the toner. The average circularity becomes smaller as the surface shape of the toner becomes more complicated. The average circularity is obtained by calculating the circularity (Ci) of each particle measured for a group of particles having a circle equivalent diameter of 3 μm or more from the following formula, and further, the sum of the circularities of all the particles measured by the following formula. Divided by the total number of particles (m) is defined as the average circularity (Ca).

[0094]

(Equation 1)

(Equation 2)

The circularity and the average circularity can be measured using a flow particle image analyzer “FPIA-1000” manufactured by Toa Medical Electronics.

The toner used in the present invention is not particularly limited, but preferably has a weight average particle diameter of 2 to 10 μm, and more preferably 5 to 9 μm in order to form a high quality image. If the weight average particle size of the toner is smaller than 2 μm, there may be a problem in developability or transferability.
If it exceeds m, the image quality tends to be inferior. The average particle size of the toner can be adjusted by the toner production conditions such as pulverization conditions in the case of a pulverization method and dispersion conditions and polymerization conditions in the case of a polymerization method. In the toner production process, it can be appropriately adjusted by performing classification after pulverization or granulation.

In the non-magnetic toner used in the present invention, the particle number% of 3.2 μm or less is preferably 10% or less. If the number% of 3.2 μm or less exceeds 10%, the transfer efficiency tends to deteriorate, and the fog tends to increase. When the magnetic toner is collected, the fine powder is mixed into the magnetic toner, and the magnetic powder is collected. The characteristics during use tend to deteriorate.

In the present invention, the above weight average particle diameter and the number% of 3.2 μm or less are determined by the coulter counter TA.
It can be measured by a type II or Coulter Multisizer (manufactured by Coulter) In this measurement, an electrolytic solution is used. As the electrolytic solution, a solution prepared as a 1% NaCl aqueous solution using primary sodium chloride can be used. For example, ISOTON R-II
(Manufactured by Coulter Scientific Japan) can also be used.

As a specific measuring method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is used as a dispersing agent in 100 to 150 ml of the electric field aqueous solution.
In addition, 2 to 20 mg of the measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic
The volume distribution and the number distribution are calculated by measuring the volume and the number of toner particles having a size of 2 μm or more using a μm aperture.
Then, a weight-based weight average particle diameter (D4) and a volume average particle diameter (Dv) obtained from the volume distribution (the median value of each channel is a representative value for each channel) can be obtained. In addition, the particle diameter in the present invention indicates the weight average particle diameter (D4).

The channels used for measuring the particle size distribution were 2.00 to less than 2.52 μm, and 2.52 to less than 2.52 μm.
3. less than 17 μm, 3.17 to less than 4.00 μm,
00 to less than 5.04 μm, 5.04 to less than 6.35 μm, 6.35 to less than 8.00 μm, 8.00 to 10.0
11. less than 8 μm, 10.08 to less than 12.70 μm,
70 to less than 16.00 μm, 16.000 to 20.20 μm
m, 20.20 to 25.40 μm, 25.40
It is preferable to use a total of 13 channels of 未 満 32.00 μm or less, 32.00 to less than 40.30 μm.

In the non-magnetic toner used in the present invention, the number% of 3.2 μm or less is 2.00 to 2.52 μm.
m, and the sum of channels less than 2.52 to 3.17 μm.

Hereinafter, the a-Si photosensitive member used in the present invention will be described.

[A-Si Photoconductor] In the present invention, a photoconductor having a conductive support and a photoconductive layer containing amorphous silicon, preferably a surface layer containing amorphous carbon is used. Further, a material having improved characteristics is used as needed.

[Layer Structure / a-Si Photoconductor] FIGS.
FIG. 2 is a schematic configuration diagram illustrating a layer configuration of a photoconductor used in the present invention.

The photosensitive member 400 shown in FIG. 4 has a photosensitive layer 402 provided on a conductive support 401 for the photosensitive member. The photosensitive layer 402 is composed of a photoconductive layer 403 made of a-Si: H, X and having photoconductivity, and an amorphous carbon-based surface layer 404.

FIG. 5 is a schematic configuration diagram for explaining another layer configuration of the photosensitive member used in the present invention. In the photoconductor 400, a photoconductive layer 402 is provided on a conductive support 401 for the photoconductor. The photosensitive layer 402 includes a photoconductive layer 403 and an amorphous carbon-based surface layer 40.
4 and the photoconductive layer 403 has a
The charge generation layer 412 and the charge transport layer 411 are made of -Si: H, X.

FIG. 6 is a schematic configuration diagram for explaining still another layer configuration of the photoreceptor used in the present invention. In the photoconductor 400, a photoconductive layer 402 is provided on a conductive support 401 for the photoconductor. The photosensitive layer 402
Is composed of a charge injection blocking layer 405 formed on a conductive support 401, a photoconductive layer 403, and an amorphous carbon-based surface layer 404. The photoconductive layer 4
Reference numeral 03 denotes a charge generation layer 412 and a charge transport layer 411 made of a-Si: H, X.

FIG. 7 is a schematic structural view for explaining still another layer constitution of the photosensitive member used in the present invention. In the photoconductor 400, a photoconductive layer 402 is provided on a conductive support 401 for the photoconductor. The photosensitive layer 402
Is formed by the charge injection blocking layer 405 formed on the conductive support 401, the photoconductive layer 403, the upper charge injection blocking layer 413 formed on the photoconductive layer 403, and the amorphous carbon-based surface layer 404. It is configured. The photoconductive layer 403 includes a charge generation layer 4 made of a-Si: H, X.
12 and a charge transport layer 411.

Examples of the method for producing the a-Si photosensitive member include a glow discharge method (an AC discharge CVD method such as a low-frequency CVD method, a high-frequency CVD method or a microwave CVD method, or a DC discharge CVD method), a sputtering method, and the like. It can be formed by various thin film deposition methods such as a vacuum evaporation method, an ion plating method, a photo CVD method, and a thermal CVD method. The glow discharge method, particularly the high-frequency glow discharge method using a power supply frequency in the RF band and the VHF band, is relatively easy to control the conditions for manufacturing the photosensitive member for an image forming apparatus having desired characteristics. It is preferably used. The production of the photoreceptor used in the present invention will be described more specifically later.

[Conductive Support] As the conductive support,
Various materials can be used, and various metals and alloys thereof, such as aluminum and stainless steel, can be used. In addition, by conducting a conductive treatment on at least the surface of the electrically insulating support on the side on which the photosensitive layer is to be formed, it is possible to form the electrically conductive support with an electrically insulating material.

The shape of the conductive support 401 can be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface. The thickness is appropriately determined so that the desired photoconductor 400 can be formed.

In particular, when performing image recording using coherent light such as laser light, the conductive support 401 is required to more effectively eliminate image defects due to so-called interference fringe patterns appearing in a visible image. May be provided with irregularities on the surface. The irregularities provided on the surface of the conductive support 401 are described in JP-A-60-168156 and JP-A-60-178457.
And JP-A-60-225854.

As another method for more effectively eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, unevenness due to a plurality of spherical trace depressions on the surface of the conductive support 401 is described. A shape may be provided. That is, the surface of the conductive support 401 has irregularities smaller than the resolution required for the photosensitive member 400, and the irregularities are caused by a plurality of spherical trace depressions. Irregularities due to a plurality of spherical trace depressions provided on the surface of the conductive support 401 are as follows:
It is produced by a known method described in JP-A-61-231561.

[Photoconductive Layer] In the present invention, the photoconductive layer contains amorphous silicon. For the amorphous silicon, a non-single-crystal material mainly containing silicon atoms is used, and a part of the amorphous silicon may have a crystal structure. Also,
In addition to silicon atoms, hydrogen atoms and halogen atoms may be contained, and atoms such as carbon atoms, nitrogen atoms and oxygen atoms may be contained.

In the present invention, the photoconductive layer 403 contains atoms for controlling the conductivity as necessary, for example, in order to provide characteristics according to the charging polarity to be used or to widen the latitude of manufacturing stability. (Doped).

In the case of doping atoms for controlling the conductivity, they may be contained in the photoconductive layer 403 in a state of being uniformly distributed or in a non-uniform distribution in the layer thickness direction. There may be parts that do.

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field.
Belonging to Group 13 of the Periodic Table that gives the conduction properties
An atom belonging to Group 15 of the periodic table (Group 15 atom) which provides n-type conduction characteristics can be used.

As the Group 13 atoms, specifically, boron (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl) and the like. First
Specific examples of group V atoms include phosphorus (P) and arsenic (A
s), antimony (Sb), bismuth (Bi) and the like.

In the present invention, the thickness of the photoconductive layer 403 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 15
It is desirable that the thickness be in the range of ６０60 μm, more preferably 18-50 μm, and most preferably 20-45 μm.

[Surface Layer] In the present invention, the photoconductive layer 40 formed on the conductive support 401 as described above is used.
3 and an amorphous carbon-based surface layer 404
Is preferably formed. The surface layer 404 has a free surface (410 in FIGS. 4 to 7), and is mainly used for achieving the object of the present invention in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability. Provided.

In the present invention, it is more preferable to use an amorphous carbon film (aC: H) mainly composed of carbon on the outermost surface. It is also effective to use an amorphous carbon film (a-C: Si, H) containing a small amount of Si atoms. Furthermore, it is also effective to use an amorphous carbon film (aC: H: F) having a bond with fluorine for the inside and / or the outermost surface.

If the outermost surface of the surface layer 404 is the above-mentioned amorphous carbon film (aC: H or aC: H: F), the lower part thereof is a well-known amorphous carbon film. Silicon (a-
SiC: H, X) or amorphous carbonized and / or oxidized and / or silicon nitride (a-SiCON: H, X)
It is preferable to use a material such as

AC: H has excellent water repellency, low friction, and high hardness equal to or higher than that of a-SiC. This has the effect of preventing blurring of the image. Further, it has excellent release properties and is effective for cleaning properties such as toner removal properties. Further, for example, the incorporation of a halogen atom such as a fluorine atom is effective for water repellency and friction reduction, and aC: H: F has more remarkable water repellency and low friction effects.

In the present invention, the surface free energy of the photoreceptor is preferably in a specific range, 35 mN / m to 65 mN / m, and the surface free energy is preferably 40 mN / m to 60 mN / m. Is more preferred.

If the surface free energy of the photoreceptor is larger than the above range, the adhesion between the photoreceptor and the toner is increased, and filming for forming a thin film on the photoreceptor may occur. This is not preferable because the load on the device tends to increase and cleaning failure tends to occur. Further, making the surface free energy smaller than the above range is considered effective for an electrophotographic apparatus,
It is difficult to manufacture both technically and economically.
N / m or more is realistic.

The surface free energy (γ) of the photoreceptor is F
Orkes's extension theory. In the following description, γ indicates the wettability of foreign substances such as toner on the surface of the photoreceptor.

The description of the surface free energy is shown below. Adhesion of foreign matter such as residual toner to the photoreceptor surface is a category of physical bonding, and is an intermolecular force (van der Waa).
ls force) is the main cause. The surface free energy (γ) captures the phenomenon caused by the intermolecular force on the outermost surface. There are roughly three types of "wetting" of substances. "Adhesion wetting" in which the substance 1 adheres to the substance 2, "extended wetting" in which the substance 1 spreads on the substance 2, and "immersion wetting" in which the substance 1 soaks or soaks in the substance 2.

Regarding the adhesion wetting, regarding the surface free energy (γ) and the wettability, the relationship between the substance 1 and the substance 2 is as follows from the Young's equation.

[0129]

(Equation 3)

In the above formula, when it is considered that foreign matter or moisture adheres to the surface of the photoreceptor in the image forming apparatus, the substance 1 may be a photoreceptor and the substance 2 may be a foreign matter. Here, with respect to wetting of the solid and liquid, which can measure the contact angle theta ₁₂ directly, as in the photosensitive member and the toner, in the case of solid and solid, not be measured contact angle theta _12. The photoreceptor and the toner according to the present invention are usually both solid, which corresponds to this case.

Yasuaki Kitazaki, Toshio Hata, et al., In the Japan Adhesion Society, 8 (3), 131-141 (1972), Forkes described non-polar intermolecular forces with respect to interfacial free energy (synonymous with interfacial tension). It has been shown that the theory can further be extended to components due to polar or hydrogen-bonding intermolecular forces. According to the extended Forkes theory, the surface free energy of each substance can be obtained in two or three components. Below, the theory of three components is described taking the case of adhesion and wetting as an example. This theory is based on the following assumptions.

[0132] 1. Addition rule of surface free energy (γ)

(Equation 4) Applying this to ForkeS theory, the interfacial free energy γ ₁₂ of the two substances is as follows.

[0133]

(Equation 5) further,

(Equation 6)

The surface free energy of the photoreceptor is p,
The surface free energy of each component d and h can be measured by using a known reagent and measuring and calculating the adhesion to the reagent. In the present invention, the reagent is pure water,
Using methylene iodide and α-bromonaphthalene, a contact angle meter CA-S ROLL manufactured by Kyowa Interface Co., Ltd. was used to measure the contact angle of each of the above reagents on the surface of the photoreceptor. It is preferable to calculate the surface free energy γ with the analysis software EG-11.

In addition to the reagents described above, those in which the components p, d, and h are appropriately combined may be used. The measurement can also be performed by a general method other than the above, such as the Wilhelmy method (hanging plate method) or the de Nui method.

The surface free energy changes depending on the fine shape of the surface, the composition and structure of the surface, the atoms appearing on the outermost surface, and the electronic state thereof. As a method of controlling the surface free energy to an arbitrary value, as the production conditions, the content of C on the outermost surface and the content of Si atoms are slightly increased, and further, the content of hydrogen and fluorine atoms, and the applied high frequency power are changed. And the like.

When the high-frequency power, the internal pressure, and the temperature of the support were kept constant, the inventors' experiments showed that the C content on the outermost surface was reduced and the Si atoms were slightly contained to reduce the surface content. We have confirmed that free energy increases. Also, as the high-frequency power was increased, the surface free energy tended to rise once and then decrease. However, since the surface active energy involves the most active outermost surface atoms, it is very difficult to control the surface free energy, and in reality, the conditions for obtaining a desired surface free energy value are determined by experiments.

Further, in the present invention, the surface layer 404 may contain atoms for controlling conductivity as necessary. As the atom for controlling the conductivity, the “group 13 atom” or the “group 15 atom” as described in the section of the photoconductive layer.
Can be used.

Carbon atoms and / or oxygen atoms and / or nitrogen atoms and atoms for controlling conductivity may be uniformly contained in the surface layer 404, or may be contained in the thickness direction of the surface layer. There may be a portion having a non-uniform distribution such that the amount changes. Further, a layer (an upper intermediate layer) in which the content of carbon atoms, oxygen atoms, and nitrogen atoms is lower than that of the surface layer can be provided between the photoconductive layer and the surface layer. In the interface region between the surface layer 404 and the photoconductive layer 403, a region where the composition varies may be provided. These are effective for improving the adhesion between the surface layer and the photoconductive layer and for improving the electrical characteristics.

The layer thickness of the surface layer 404 is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is easily lost due to abrasion or the like during use of the photoreceptor, and if it exceeds 3 μm, a decrease in electrophotographic characteristics such as an increase in residual potential may be observed. is there.

With the structure of the surface layer as described above, the electrical characteristics and high-speed continuous usability can be significantly improved, and a higher hardness of the surface layer can be secured.

[Charge Injection Blocking Layer] In the photoreceptor used in the present invention, a conductive support 401 and a photoconductive layer 403 are provided.
And a charge injection blocking layer 405 (lower injection blocking layer UBL; Under Blocking Layer) having a function of blocking charge injection from the conductive support 401 side.
r), and between the photoconductive layer 403 and the surface layer 404, an upper charge injection blocking layer 413 (an upper injection blocking layer TBL; Top B) which functions to prevent charge injection from the surface layer side.
A locking layer may be provided. These charge injection blocking layers have a function of preventing charges from being injected from the support side or the surface layer side to the photoconductive layer side when the photosensitive layer is subjected to a charging treatment of a fixed polarity on its free surface. are doing.

As the atoms for controlling the conductivity contained in the charge injection blocking layer, the same atoms as those described for the photoconductive layer can be used. In the present invention, the thickness of the lower charge injection blocking layer is preferably from 0.05 to 5 μm, more preferably from 0.1 to 4 μm, from the viewpoint of obtaining desired electrophotographic characteristics and economic effects. Is desirably 0.5 to 3 μm. The thickness of the upper charge injection blocking layer is preferably from 0.01 to 3 μm, more preferably from 0.03 μm, from the viewpoint of obtaining desired electrophotographic characteristics and economic effects.
２2 μm, optimally 0.05-1 μm.

In addition, it has other functions such as an adhesion layer for the purpose of further improving the adhesion and a light absorbing layer for preventing the occurrence of interference patterns due to light reflected from the conductive support. A layer may be provided.

[A-Si Photoreceptor Manufacturing Apparatus] Next, when producing the photoreceptor used in the present invention, a deposition film forming apparatus and a deposition apparatus for forming various amorphous material films used for the above-mentioned photosensitive layer. The film forming method will be described in more detail.

FIG. 2 is a schematic diagram showing an example of an apparatus for manufacturing a photosensitive member used in the present invention by a high-frequency plasma CVD method (hereinafter abbreviated as "RF-PCVD") using an RF band as a power supply frequency. It is. The configuration of the manufacturing apparatus shown in FIG. 2 is as follows.

This apparatus is roughly classified into a deposition apparatus (210
0), source gas supply device (2200), reaction vessel (21)
11) It is composed of an exhaust device (not shown) for reducing the pressure inside. A cylindrical conductive support (211) is provided in a reaction vessel (2111) in the deposition apparatus (2100).
2), a heater for heating the support (2113), a source gas introduction pipe (2114), and a high-frequency matching box (2115) are connected.

The source gas supply device (2200) is made of SiH
_Four, Si_TwoH_TwoCl_Two, H_Two, CH_Four, B _TwoH₆, PH_ThreeOriginal field
Source gas cylinder (2221-222) in which the feed gas is enclosed.
6) and a raw material gas cylinder valve (2231-2236),
Gas inflow valve (2241-2246), gas outflow valve
(2251-2256) and mass flow controller
-(2211 to 2216), each raw material gas
Cylinder reacts via source gas introduction valve (2260)
Connected to the source gas inlet pipe (2114) in the container (2111).
Has been continued.

The formation of a deposited film using this apparatus can be performed, for example, as follows. First, the reaction vessel (21
11), a conductive support (2112) is set in the reaction vessel (2112) by an exhaust device (for example, a vacuum pump) (not shown).
11) Exhaust the inside. Subsequently, the temperature of the conductive support (2112) is controlled to a predetermined temperature of 200 ° C to 350 ° C by the support heating heater (2113).

The raw material gas for forming the deposited film is supplied to the reaction vessel (21).
11), the raw material gas cylinder valve (22)
31 to 2236), a leak valve of the reaction vessel (211).
7) is closed, and a gas inflow valve (2241-2246) and a gas outflow valve (225)
1-2256), and confirming that the source gas introduction valve (2260) is open, firstly, the main valve (211).
8) is opened to evacuate the reaction vessel (2111) and the source gas pipe (2116).

Next, the reading of the vacuum gauge (2119) was about 5 × 1.
When the pressure becomes 0 ^-4 Pa, the source gas introduction valve (226)
0), close the gas outflow valves (2251-2256).

Thereafter, the raw material gas cylinders (2221-222)
26) Each gas was converted to a raw material gas cylinder valve (2231-
2236) is opened and introduced, and the pressure regulators (2261-2) are introduced.
266), each gas pressure is set to 2 kg / cm ² (1.96 ×
It is adjusted to 10 ⁴ Pa). Next, the gas inflow valve (22
41 to 2246) are gradually opened, and each gas is introduced into the mass flow controllers (2211 to 2216).
After the preparation for film formation is completed as described above, each layer is formed by the following procedure.

When the temperature of the conductive support (2112) reaches a predetermined temperature, the gas outflow valves (2251-2256)
And the source gas introduction valve (226)
0) is gradually opened, and the raw material gas cylinders (2221-222) are opened.
From 6), a predetermined gas is introduced into the reaction vessel (2111) via the raw material gas introduction pipe (2114). Next, each raw material gas is adjusted by a mass flow controller (2211 to 2216) so as to have a predetermined flow rate. At this time, the opening of the main valve (2118) is adjusted while watching the vacuum gauge (2119) so that the pressure in the reaction vessel (2111) becomes a predetermined pressure of 133 Pa or less.

When the internal pressure becomes stable, the frequency becomes 13.5.
A 6-MHz RF power supply (not shown) is set to a desired power, and RF power is introduced into the reaction vessel (2111) through the high-frequency matching box (2115) to generate glow discharge. The raw material gas introduced into the reaction vessel is decomposed by the discharge energy, and the conductive support (21
12) A deposited film mainly containing predetermined silicon is formed thereon. After the desired film thickness is formed,
The supply of RF power is stopped, the outflow valve is closed, and the flow of gas into the reaction vessel is stopped, thereby completing the formation of the deposited film.

By repeating the same operation a plurality of times, a photosensitive layer having a multilayer structure including a desired photoconductive layer and a surface layer is formed.

When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed, and each gas is supplied to the reaction vessel (211).
1) Close the gas outflow valves (2251 to 2256) and set the raw material gas introduction valve (2260) to avoid remaining in the piping from the gas outflow valves (2251 to 2256) to the reaction vessel (2111). The operation of opening and further opening the main valve (2118) to once evacuate the reaction vessel to a high vacuum is performed as necessary.

In order to make the film formation uniform, it is also effective to rotate the conductive support (2112) at a predetermined speed by a driving device (not shown) during the layer formation. .

Further, it goes without saying that the above-mentioned gas types and valve operations are changed according to the production conditions of each layer.

The temperature of the conductive support during the formation of the deposited film is in particular 200 to 350 ° C., preferably 230 to 3 ° C.
30 ° C., more preferably 250 to 310 ° C. The heating method of the conductive support may be any heating element having a vacuum specification, and more specifically, an electric resistance heating element such as a winding heater of a sheath heater, a plate heater, a ceramic heater, a halogen lamp, and an infrared lamp. And the like, and a heating element using a heat exchange means using a liquid, a gas, or the like as a heating medium. The surface material of the heating means is
Metals such as stainless steel, nickel, aluminum, copper, etc.
Ceramics, heat-resistant polymer resins and the like can be used.

In addition, a method is also used in which a container dedicated to heating is provided in addition to the reaction container, and after heating, the conductive support is transported into the reaction container in a vacuum.

FIG. 3 shows an example of a high-frequency plasma CVD method (referred to as "VHF-PCVD") using a VHF band. This apparatus is a deposition apparatus (210
0) is replaced with a movable deposition device (3100) shown in FIG. 3 and connected to a source gas supply device (not shown),
This is an example in which the manufacturing apparatus is a VHF-PCVD method. This apparatus is, for example, in a plant provided with facilities for performing various processes in each area, a mobile type deposition apparatus in which after performing each process in each area, the process is moved to the next process area and the next process is performed. is there.

The movable deposition device (3100) is mainly made of SUS
(3102), a cylindrical reaction vessel (3101) made of Al alloy, a reaction vessel support (3202),
It comprises a gate valve (3203) for connecting the exhaust part and a caster (3201) for moving. In the reaction vessel (3101), six conductive supports (311
2) and a heater for heating the support (3113) are arranged,
Further, one source gas introduction pipe (3114) is arranged. In addition, six SUS rod-shaped high-frequency electrodes (3111) are arranged at equal intervals on a concentric circle, and a high-frequency power supply (312) is provided via a high-frequency matching box (3120).
1) is connected.

As preparation for forming a deposited film, for example, in a heating area in a plant, a movable deposition device (3100)
The exhaust-port connection gate valve (3203) is connected to an exhaust device to heat the cylindrical conductive support to a predetermined temperature.
Control, and then the exhaust connection gate valve (320
3) is disconnected, the movable deposition device (3100) is moved to the film formation area in the plant, and the exhaust valve connection gate valve (3203) is connected to the exhaust device in the film formation area to fix the connection. The gate valve for exhaust connection (32
03) and open the exhaust device side gate valve (not shown)
The inside of the movable deposition device (3100) is evacuated.

In forming the deposited film, the source gas introduction pipe (31)
Source gas is introduced into the reaction vessel (3101) via 14). The flow rate of the raw material gas is set to a set flow rate, a glow discharge is generated in the reaction vessel (3101), and the raw material gas is excited and dissociated to form a deposited film on the conductive support (3112). During the deposition film production, the support rotation motor (3
115) is driven to rotate the conductive support (3112).

After the formation of the desired film thickness, the supply of the high-frequency power is stopped, the supply of the source gas is stopped, and the formation of the deposited film is completed. In the case of forming a multilayered deposited film, the same operation is repeated a plurality of times.

[0166]

EXAMPLES Hereinafter, the effects of the present invention will be specifically shown by way of examples, and the present invention will be specifically described. Note that the present invention is not limited to these examples and the like.

Embodiments 1 to 6 FIG. 1 is a sectional view of an electrophotographic apparatus used in Embodiments 1 to 6. Photoconductor 102
Has a photoconductive layer containing amorphous silicon and an amorphous carbon surface layer on a conductive support, and its surface free energy was 57 mN / m. The photoreceptor rotates in the direction of arrow A, and a corona charger (charging means) 1
01, the photoconductor 102 is charged. In the exposure, an electrostatic latent image is formed by turning on / off the photosensitive member 102 on the photosensitive member 102 according to digital image information.

For developing the formed electrostatic latent image, a plurality of developing units 104 (a) to 104 (d) are used to apply black toner, magenta toner, cyan toner and yellow toner to the photosensitive member 1.
02 to form a toner image. The toner image is transferred onto the intermediate transfer member 122 for each color,
A color superimposed color development image of four colors is formed on 2. Photoconductor 202
The upper transfer residual toner is separated into a collected toner and a waste toner by a collection / separation unit (not shown) in the cleaner unit 107, and is sent to respective transport paths.

After transferring the toner image from the intermediate transfer member 122 to the recording material P, the surface of the intermediate transfer member is cleaned by the intermediate transfer material cleaning means 123.

In this embodiment, a two-component developer containing a non-magnetic toner and a magnetic carrier is used for the color toners of the magenta toner, the cyan toner, and the yellow toner, and the developing devices 104 corresponding to each of these color toners are used.
(B) to (d) use a two-component developing device. Further, a one-component magnetic developer containing a magnetic toner is used for the black toner, and a magnetic one-component developer 1 is used for the black toner developing device 104 (a).
04 is used.

The recovery / separation means was used as an example of the recovery / separation means of the present invention, as shown in FIG.

The amorphous silicon photoreceptor shown in FIG.
It was manufactured by forming a charge injection blocking layer, a photoconductive layer, and a photosensitive layer including a surface layer on a mirror-finished aluminum cylinder having an outer diameter of 80 mm using an F-PCVD apparatus. Table 1 shows the manufacturing conditions.

[0173]

[Table 1]

In this embodiment, toners of combinations B to G in Table 2 below, which show combinations of the circularity and the average circularity of the toner, were used. In this embodiment,
For magnetic toner, pulverized toner is used for toner having a circularity of less than 0.970, and for non-magnetic toner,
A suspension polymerization toner was used as the toner having a particle size of 0.960 or more.

[0175]

[Table 2]

The recovery rate in the recovery / separation means when using the toner of the above combination and the mixing rate of the non-magnetic toner contained in the magnetic toner were evaluated. The recovery rate and the mixing ratio will be described below. Table 3 shows the evaluation results.

(1) Collection rate Black and white image (CanonTestSheetNA-C1)
A full-color image (CanonTestS) is defined assuming that the amount of magnetic toner that can be collected when 10,000 copies are continuously made is 100.
The rate of the amount of magnetic toner collected when 10,000 sheets of heat CA-4) were continuously copied was defined as the recovery rate. That is, the recovery rate is represented by the following equation.

(Equation 7)

(2) Incorporation Rate Evaluation was made based on the mass ratio of the nonmagnetic toner contained in the collected toner. The case where the collected toner was only the magnetic toner was determined as 100%. The mixing ratio was represented by the following equation, and the calculated result was evaluated according to the following criteria.

(Equation 8) ◎ (good): 3.0% or less (good as reused toner) ○ (acceptable): 3.0 to 7.0% (practicable as reused toner) △ (bad): 7.0% or more

[0179]

[Table 3]

When the toner of the above combination is used, the initial evaluation image and the evaluation image after the output of 10,000 sheets of images are used, when the collected toner is not reused and when it is reused. The following items were measured and evaluated respectively. Table 4 shows the evaluation results.

(3) Fog The reflectivity of a solid white image in a proper image was measured, and the reflectivity of an unused transfer paper was further measured. Δ (worst value of the reflectivity of a solid white image) − (unused transfer The average value of the reflectance of paper) was defined as fog density, and the evaluation results were shown by the following indices (however, the reflectance was measured at 10 points at random). The reflectance was measured by TC-6DS (manufactured by Tokyo Denshoku). A: less than 1.0% (fogging is not visually observed) B: 1.0 to 2.0% (fogging is not recognized unless watching) C: 2.0 to 4.0% (fogging is not recognized) D: 4.0 to 5.0% (fog is noticeable but practical use is possible) E: Over 5.0% (fog is noticeable and practically difficult to use)

(4) Image quality A: A clear image with no scattering even when viewed with a loupe B: A clear image as seen visually C: Slightly scattering, but no practical problem D: In addition to scattering Sharp characters are noticeable

(5) Density gradation A: An image with good reproducibility from a white background to a black background including a halftone B: Degree of slight roughness observed even in a highlight part C: Roughness in halftone part Although there is no problem in practical use D: There is also roughness in the solid part

[0184]

[Table 4]

As can be seen from the evaluation results, the use of a non-magnetic toner having an average circularity of 0.960 or more has little change in fog, image quality and density gradation at initial and after image output.
High quality images are obtained. Also collects magnetic toner,
It was found that in the case of reproduction, the magnetic toner can be efficiently separated and collected. Furthermore, the change in fog, image quality and density gradation at the initial stage and after image output is small, and a high quality image is obtained.

Therefore, the non-magnetic toner using the photoreceptor having the above-mentioned surface free energy and having the circularity, the number ratio, and the average circularity within the above-mentioned ranges can reduce the deterioration of the toner as the reused toner. It was found that high quality images could be obtained.

[Comparative Example 1] The same test as in Example 1 was performed using the combinations shown in Table 4. As a result, fog, image quality, and density gradation were inferior.

Embodiments 7 to 12 Non-magnetic one-component developers are used for the magenta toner, cyan toner, and yellow toner color toner, and the developing devices 104 (b) to 104 (d) corresponding to the respective color toners are used. )), According to the conditions shown in Table 4, except that a non-magnetic one-component developing device was used.
A test was conducted in the same manner as in Examples 1 to 6 in which the magnetic toner was reused. With respect to the recovery rate of the magnetic toner and the mixing rate of the non-magnetic toner, the same results as in Table 3 were obtained.
As for the evaluation of the evaluation image, the results shown in Table 4 were obtained.

The evaluation results show that the magnetic toner has a circularity of 0.
A toner having a toner content ratio of 900% or more and less than 0.970 and a toner number ratio of 80% or more is used.
It was found that the use of a material having a value of 0 or more resulted in a low mixing ratio and a collection ratio of 70% or more, and the toner can be efficiently collected and reproduced. Furthermore, the change in fog, image quality and density gradation at the initial stage and after image output is small, and a high quality image is obtained.

Therefore, in the non-magnetic toner using the photoreceptor having the above surface free energy and the circularity, the number ratio, and the average circularity in the above-mentioned ranges, the deterioration of the reused toner is reduced. It was found that high quality images could be obtained.

[Comparative Example 2] A test similar to that of Example 7 was performed using the combinations in Table 4 and found to be inferior in fog, image quality, and density gradation.

[Examples 13 to 20] The effect on the recovery rate of the magnetic toner when the photoconductors having different surface free energies were used instead of the photoconductors used in the above-described Examples and Comparative Examples was examined. The surface free energy of the photoconductor was adjusted by appropriately changing the manufacturing conditions of the surface layer of the photoconductor. More specifically, the content of Si atoms in the surface layer, the added amount of H ₂ gas, and the value of RF power were changed, and as shown in Table 5, several types of amorphous carbon-based surface layers having different surface free energies were used. A photoreceptor was prepared.

[0193]

[Table 5]

Evaluation was performed in the same manner as in Example 7 using each photosensitive member. As for the toner, a toner having a circularity of 0.900 or more and less than 0.950 and a toner number ratio of 80% or more produced by a pulverization method is used as a magnetic toner, and an average circularity produced by a suspension polymerization method is 0.980. And 3.2
A non-magnetic toner having a number% of μm or less of 6% was used. Table 6 shows the evaluation results of the evaluation images, and Table 7 shows the evaluation results of the recovery rate of the magnetic toner and the mixing rate of the non-magnetic toner.
Are shown below.

[0195]

[Table 6]

[0196]

[Table 7]

The difference in fog, image quality, and density gradation even when the same toner is used is considered to be due to the difference in free energy on the surface of the photoreceptor.

From the evaluation results, it was found that the surface free energy was 35
To 65 mN / m, more preferably 40 to 60 mN / m
By setting m, the recovery rate is improved. Therefore,
It was found that the use of the photoreceptor having the surface free energy in the above-mentioned range reduced the deterioration of the reused toner and provided a high-quality image.

However, in Examples 13 and 14, slight image streaks due to poor cleaning were observed. This is probably because the surface free energy was too small. In Examples 19 and 20, the cleaning blade squeak was observed during the durability test. This is probably because the surface free energy was too high.

Example 21 The same photoreceptor as in Example 7 was used. The black toner used was a magnetic toner prepared by a suspension polymerization method and having a circularity of 0.900 or more and less than 0.970 in which the ratio of the number of toners was 80% or more. For the yellow, cyan, and magenta color toners, a nonmagnetic toner having an average circularity of 0.98 produced by the suspension polymerization method and a number% of 3.2 μm or less of 5 to 6% is used. Was.

In the electrophotographic apparatus, when the RGB signals read from a full-color original by a scanner are converted into CYMK signals, the original ratio (with respect to the original size) of the K (black toner) component is calculated. Depending on the value of
The same electrophotographic apparatus as in Example 7 was used except that the recovery path on-off valve arranged in the cleaning means was modified to open and close.

The original ratio was 100% when the original was a solid black original, that is, when the entire surface of the original was developed with only black toner, and 0% when no black toner was used.

Full-color originals having different K component original ratios were continuously copied and output on 10,000 sheets. The manuscript had a character image portion of K component (original ratio 25%) on the background of only the C component of the CYM component. At that time, the recovery rate and the mixing rate of the black toner were evaluated. FIG. 10 shows the evaluation results.

FIG. 10 shows that the collection ratio is approximately 2%.
You can see that it rises from about%. Also, the mixing ratio becomes 3% or less after the document ratio exceeds 2%. The mixing ratio of 7% or less for obtaining a practical recovered toner is when the original document ratio is approximately 1% or more.

As described above, the collection path opening / closing valve is opened / closed when the document ratio is about 2%. For example, at 2% or less, it is understood that the quality of the collected toner can be used in a good state by leading the toner to the disposal route without collecting the toner.

[Embodiment 22] RF-PCVD shown in FIG.
An amorphous silicon photoreceptor was manufactured under the conditions shown in Table 8 on a mirror-finished aluminum cylinder having a diameter of 80 mm (φ80) using an apparatus for producing a photoreceptor for an electrophotographic apparatus by a method. The surface free energy at that time is 4
It was 8 mN / m.

[0207]

[Table 8]

As the electrophotographic apparatus, the electrophotographic apparatus used in Example 21 in which the operation of the recovery path opening / closing valve was set to 2% of the original ratio was used. The prepared photoreceptor was set in the above electrophotographic apparatus and used.

As the black toner, a magnetic toner produced by a pulverization method and having a circularity of 0.900 or more and less than 0.970 so that the ratio of the number of toners was 80% or more was used. For yellow, cyan and magenta toners,
A non-magnetic toner having an average circularity of 0.98 and a number% of 3.2 μm or less of 5 to 6% prepared by a suspension polymerization method was used.

As a result of performing the same evaluation as in Example 7, good results were obtained in all of the recovery rate, the mixing rate, the fog, the image quality, and the density gradation.

That is, an amorphous silicon photosensitive member having an amorphous surface layer mainly composed of carbon having a surface free energy of 35 to 65 mN / m, and a circularity of 0.
The use of a magnetic toner in which the toner in the range of 900 to less than 0.970 is 80% or more and a non-magnetic toner having an average circularity of 0.970 or more enables the magnetic toner alone to be separated and collected and reused. Electrophotographic equipment
It has been found necessary to obtain high quality images.

[Embodiment 23] RF-PCVD shown in FIG.
Using an apparatus for manufacturing a photoreceptor for an electrophotographic apparatus by a method, wherein an aC-based surface layer is laminated on the outermost surface side of a SiC-based surface layer on an aluminum cylinder having a mirror-finished surface with a diameter of 80 mm (φ80). Was prepared. At that time, the surface layer was provided with a region where the SiH ₄ / CH ₄ gas was continuously changed so as to be continuous with the photoconductive layer in order to prevent interference of coherent light.
The outermost surface was an amorphous carbon-based surface layer containing a slight amount of Si atoms. Table 9 shows the manufacturing conditions. The surface free energy of this photoreceptor was 59 mN / m.

[0213]

[Table 9]

The electrophotographic apparatus used in Example 21 was used. The operation of the recovery path on-off valve was set to 1.2%. The prepared photoreceptor was used in the above electrophotographic apparatus. The same toner as in Example 21 was used as the toner.

As a result of performing the same evaluation as in Example 7, good results were obtained in all of the recovery rate, the mixing rate, the fog, the image quality, and the density gradation.

That is, an amorphous silicon photosensitive member having an amorphous surface layer mainly composed of carbon having a surface free energy of 35 to 65 mN / m, and a circularity of 0.
The use of a magnetic toner in which the toner in the range of 900 to less than 0.970 is 80% or more and a non-magnetic toner having an average circularity of 0.970 or more enables the magnetic toner alone to be separated and collected and reused. Electrophotographic equipment
It has been found necessary to obtain high quality images.

[Embodiment 24] RF-PCVD shown in FIG.
Using an apparatus for manufacturing a photoreceptor for an electrophotographic apparatus by a method, an aluminum cylinder slightly mirror-finished with a diameter of 80 mm (φ80) and a-C containing a small amount of silicon atoms
A photoreceptor having a laminated surface layer was prepared. Table 1 shows the fabrication conditions
0 is shown. The surface free energy of this photoreceptor is 62 mN
/ M.

[0218]

[Table 10]

[0219] The electrophotographic apparatus used in Example 21 was used. The operation of the recovery path on-off valve was set to 1.8%. The prepared photoreceptor was used in this electrophotographic apparatus. Example 21 was applied to the toner.
The same one was used.

As a result of performing the same evaluation as in Example 7, good results were obtained in all of the recovery rate, the mixing rate, the fog, the image quality, and the density gradation.

That is, an amorphous silicon photosensitive member having an amorphous surface layer mainly composed of carbon having a surface free energy of 35 to 65 mN / m and a circularity of 0.
The use of a magnetic toner in which the toner in the range of 900 to less than 0.970 is 80% or more and a non-magnetic toner having an average circularity of 0.970 or more enables the magnetic toner alone to be separated and collected and reused. Electrophotographic equipment
It has been found necessary to obtain high quality images.

[Embodiment 25] RF-PCVD shown in FIG.
Hydrogen gas was also introduced during the surface layer deposition onto a mirror-finished aluminum cylinder with a diameter of 108 mm (φ108) to dilute the SiH ₄ / CH ₄ gas, using an electrophotographic photoreceptor manufacturing apparatus by the EB method. Thus, a photoreceptor having an aC-based surface layer slightly containing silicon atoms was formed. Table 11 shows the manufacturing conditions. The surface free energy of this photoreceptor was 64 mN / m.

[0223]

[Table 11]

As the electrophotographic apparatus, the electrophotographic apparatus used in Example 7 was modified so that a photosensitive member of φ108 could be used. The photosensitive member produced in the above electrophotographic apparatus was set and used, and the same cleaning means as in Example 1 was used. The same toner as in Example 21 was used as the toner.

As a result of performing the same evaluation as in Example 7, good results were obtained in all of the recovery rate, the mixing rate, the fog, the image quality, and the density gradation.

That is, an amorphous silicon photosensitive member having an amorphous surface layer mainly composed of carbon having a surface free energy of 35 to 65 mN / m, and a circularity of 0.
The use of a magnetic toner in which the toner in the range of 900 to less than 0.970 is 80% or more and a non-magnetic toner having an average circularity of 0.970 or more enables the magnetic toner alone to be separated and collected and reused. Electrophotographic equipment
It has been found necessary to obtain high quality images.

[Embodiment 26] RF-PCVD shown in FIG.
A charge injection blocking layer, a photoconductive layer, an upper charge injection blocking layer, and an aC-based surface on a mirror-finished aluminum cylinder having a diameter of 80 mm (φ80) using an apparatus for manufacturing a photoreceptor for an electrophotographic apparatus by a method. An amorphous silicon photoreceptor for negative charging in which layers were laminated was produced. Table 12 shows the manufacturing conditions. The surface free energy of this photoreceptor was 36 mN / m.

[0228]

[Table 12]

As an electrophotographic apparatus, Embodiment 21
The electrophotographic apparatus used in the above was modified for negative charging. The photosensitive member produced in the above electrophotographic apparatus was set and used. The same toner as in Example 21 was used as the toner.

As a result of performing the same evaluation as in Example 7, good results were obtained in all of the recovery rate, the mixing rate, the fog, the image quality, and the density gradation.

That is, an amorphous silicon photosensitive member having an amorphous surface layer mainly composed of carbon having a surface free energy of 35 to 65 mN / m, and a circularity of 0.
The use of a magnetic toner in which the toner in the range of 900 to less than 0.970 is 80% or more and a non-magnetic toner having an average circularity of 0.970 or more enables the magnetic toner alone to be separated and collected and reused. Electrophotographic equipment
It has been found necessary to obtain high quality images.

[Embodiment 27] The VHF-PCV shown in FIG.
Using an apparatus for manufacturing a photoreceptor for an electrophotographic apparatus by the method D, a photoreceptor having an aC-based surface layer laminated on an aluminum cylinder having a mirror-finished surface with a diameter of 80 mm (φ80) was produced. Table 13 shows the manufacturing conditions. The surface free energy of this photoreceptor was 41 mN / m.

[0233]

[Table 13]

As the electrophotographic apparatus, the electrophotographic apparatus used in Example 21 was used. The prepared photoreceptor was used in the above electrophotographic apparatus. The same toner as in Example 21 was used as the toner.

As a result of performing the same evaluation as in Example 7, good results were obtained in all of the recovery rate, mixing rate, fog, image quality, and density gradation.

That is, an amorphous silicon photosensitive member having an amorphous surface layer mainly composed of carbon having a surface free energy of 35 to 65 mN / m, and a circularity of 0.
The use of a magnetic toner in which the toner in the range of 900 to less than 0.970 is 80% or more and a non-magnetic toner having an average circularity of 0.970 or more enables the magnetic toner alone to be separated and collected and reused. Electrophotographic equipment
It has been found necessary to obtain high quality images.

[Embodiment 28] The VHF-PCV shown in FIG.
Using an apparatus for manufacturing a photoreceptor for an electrophotographic apparatus by the method D, a photoreceptor having an aC-based surface layer laminated on an aluminum cylinder having a mirror-finished surface with a diameter of 80 mm (φ80) was produced. At that time, the surface layer was provided with a region where the SiH ₄ / CH ₄ gas was continuously changed so as to be continuous with the photoconductive layer in order to prevent interference of coherent light. Table 14 shows the manufacturing conditions.
The surface free energy of this photoreceptor was 52 mN / m.

[0238]

[Table 14]

As an electrophotographic apparatus, Embodiment 21
Instead of the electrophotographic apparatus used in the above, an apparatus using a cylindrical transfer drum as an intermediate transfer body was used as shown in FIG.
Other configurations are the same as those of the electrophotographic apparatus used in the twenty-first embodiment.
%. The photoreceptor produced in the above-mentioned evaluation machine was set and used.

As the black toner, a magnetic toner produced by a suspension polymerization method and having a circularity of 0.900 or more and less than 0.970 and a toner number ratio of 80% or more was used. yellow,
Each of the cyan and magenta toners is a non-magnetic toner produced by a suspension polymerization method and has an average circularity of 0.98 units.
The one having a number% of 2 μm or less of 4 to 6% was used.

As a result of performing the same evaluation as in Example 7, good results were obtained in all of the recovery rate, the mixing rate, the fog, the image quality, and the density gradation.

That is, an amorphous silicon photosensitive member having an amorphous surface layer mainly composed of carbon having a surface free energy of 35 to 65 mN / m and a circularity of 0.
The use of the magnetic toner in which the toner in the range of 900 to less than 0.970 is 80% or more and the non-magnetic toner having the average circularity of 0.970 or more enables the magnetic toner alone to be separated and collected for reuse. It has been found that the electrophotographic apparatus is necessary for obtaining a high quality image.

[Embodiment 29] The VHF-PCV shown in FIG.
Photoreceptor obtained by laminating an aC-based surface layer containing a small amount of Si atoms on a mirror-finished aluminum cylinder having a diameter of 80 mm (φ80) using a manufacturing apparatus for a photoreceptor for an electrophotographic apparatus by Method D. Was prepared. An amorphous silicon photoconductor was manufactured under the conditions shown in Table 15. The surface free energy of this photoreceptor was 59 mN / m.

[0244]

[Table 15]

As the electrophotographic apparatus, an apparatus using a cylindrical transfer drum as an intermediate transfer body as shown in FIG. 8 was used instead of the evaluation machine of Example 7. The same electrophotographic apparatus as in Example 28 was used except that the operation of the recovery path opening / closing valve was set to the original document ratio of 1.8%, and the produced photoreceptor was set and used in this electrophotographic apparatus.

As the black toner, a magnetic toner produced by a pulverization method and having a circularity of 0.900 or more and less than 0.970 so that the ratio of the number of toners was 80% or more was used.
Yellow, cyan, and magenta toners are non-magnetic toners produced by a suspension polymerization method and have an average circularity of 0.9.
Eight units whose number% of 3.2 μm or less was 4 to 6% were used.

As a result of performing the same evaluation as in Example 7, good results were obtained in all of the recovery rate, the mixing rate, the fog, the image quality, and the density gradation.

That is, an amorphous silicon photosensitive member having an amorphous surface layer mainly composed of carbon having a surface free energy of 35 to 65 mN / m and a circularity of 0.
The use of a magnetic toner in which the toner in a range of 900 to less than 0.970 is 80% or more and a non-magnetic toner having an average circularity of 0.960 or more enables the magnetic toner alone to be separated and collected and reused. Electrophotographic equipment
It has been found necessary to obtain high quality images.

[0249]

According to the electrophotographic method of the present invention, in a digital electrophotographic apparatus capable of high-speed monochrome output and high-quality full-color output, the efficiency of black toner recovery and reuse is high,
A high-quality image can be output with high stability, and a resource-saving and energy-saving electrophotographic apparatus can be obtained.

In particular, according to the present invention, the electrophotographic photoreceptor
A photoconductive layer containing at least amorphous silicon and a surface layer having at least the outermost surface made of an amorphous material containing carbon as a main constituent element and having a surface free energy of 3
By using a photoreceptor of 5 mN / m to 65 mN / m, the toner recovery rate is improved, and a non-magnetic toner having a mean circularity of 0.960 or more is used as a color toner, and a circular toner is used as a black toner. By using the magnetic toner in which the number of pieces of 0.900 or more and less than 0.970 is 80% or more, the magnetic toner and the non-magnetic toner using the magnet roller of the cleaning means can be removed without adding a complicated toner separating means. Since separation can be performed efficiently and toner deterioration of the recovered magnetic toner is reduced, a high-quality image can be stably obtained even if only the magnetic toner is supplied to the developing unit and reused for development. .

Further, by setting the surface free energy within the above range, troubles of the cleaning means were reduced.
Further, since the collected toner and the waste toner are only the same kind of toner, the conveyance is easy, and the trouble in the conveyance path is reduced.

Therefore, by adopting the constitution of the electrophotographic method of the present invention, the problem in the conventional electrophotographic method can be solved, and the toner can be efficiently reused.
An extremely high quality image can be output stably.

Further, in the present invention, when a photoreceptor whose outermost surface is made of amorphous carbon is used, the releasability of the toner is further improved, so that the transfer efficiency and the cleaning property are improved. Is even more effective.

In the present invention, when the surface free energy of the photoreceptor is set to 40 to 60 mN / m, the separation and recovery rate of the magnetic toner is further improved, the deterioration of the reused toner is suppressed, and the recovery rate of the toner is reduced. It is even more effective from the viewpoint of improvement and formation of high quality images.

In the present invention, when the weight average particle diameter of the non-magnetic toner is 5 to 9 μm and the number% of 3.2 μm or less is 10% or less, the recovery rate of the toner is improved and the image quality is high. Is more effective from the viewpoint of the formation of

In the present invention, when an intermediate transfer member such as an endless transfer belt or a transfer drum is used as a transfer material for receiving a toner image transferred from a photoreceptor, foreign matter such as paper dust comes into direct contact with the photoreceptor. This is more effective in preventing foreign matter from being mixed into the collected toner.

In the present invention, when the magnetic toner is a one-component toner and the non-magnetic toner is a two-component toner,
It is even more effective.

In the present invention, if a magnet is used as the magnetic toner collecting means, it is more effective to separate the toner with a simple configuration. Further, if the collection unit using the magnet also functions as the cleaning unit, it is more effective in separating and collecting the toner more efficiently.

In the present invention, the ratio of the original of the magnetic toner to the image to be formed is calculated, and the recovery of the magnetic toner is controlled in accordance with the calculation result. Is even more effective.

In the present invention, if the recovered toner is used after being mixed with new toner, it is effective in maintaining good quality of the magnetic toner, and is stable in high quality image. Is even more effective in forming

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of the electrophotographic apparatus of the present invention.

FIG. 2 is a diagram illustrating an example of an RF-PCVD apparatus.

FIG. 3 is a diagram showing an example of a VHF-PCVD apparatus.

FIG. 4 is a schematic configuration diagram illustrating an example of a layer configuration of the electrophotographic photoconductor of the present invention.

FIG. 5 is a schematic configuration diagram for explaining another example of the layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 6 is a schematic configuration diagram for explaining another example of the layer configuration of the electrophotographic photoconductor of the present invention.

FIG. 7 is a schematic configuration diagram for explaining another example of the layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 8 is a cross-sectional view showing an example using a cylindrical intermediate transfer member in the electrophotographic apparatus of the present invention.

FIG. 9 is a diagram illustrating an example of a cleaning unit including a separating unit according to the present invention.

FIG. 10 is a graph showing a relationship between a recovery rate and a mixing rate of black toner used in the present invention.

[Explanation of symbols]

101, 501 Charging means 102, 502, 602 Photoconductor 103 Image signal light 104 Developing means 104 (a), 504 (a), 604 (a) First developing device 104 (b), 504 (b), 604 (b) ) Second developing device 104 (c), 504 (c), 604 (c) Third developing device 104 (d), 504 (d), 604 (d) Fourth developing device 105 Paper supply system 106 (a) Transfer Means 106 (b) Separation means 107, 506, 607 Cleaning means (cleaner) 108 Static elimination means 109 Internal electrometer 110 Transport system 111 Fixing means 112 Fixing roller 113 Document 114 Document table 115 Light source 116 Scanner 117 Image signal light source 118 Mirror 119 Supply Paper path 120 Register roller 121 Drive system 122, 522, 622 Intermediate transfer material (intermediate transfer body) 1 3, 523, 623 Intermediate transfer material cleaning means 124 Intermediate transfer material cleaning blade A Photoconductor surface traveling direction P Recording material (paper) 2100 Deposition device 2111, 3101 Reaction vessel 2112, 3112 Conductive support 2113, 3113 Support Heating heater 2114, 3114 Source gas introduction pipe 2115, 3120 High frequency matching box 2116 Source gas pipe 2117 Leak valve 2118 Main valve 2119 Vacuum gauge 2200 Source gas supply device 2211-2216 Mass flow controller 2221-2226 Source gas cylinder 2231-2236 Source gas cylinder valve 2241 to 2246 Gas inflow valve 2251 to 2256 Gas outflow valve 2261 to 2266 Pressure regulator 2260 Source gas introduction valve 310 0 movable deposition apparatus 3102 shield 3111 high-frequency electrode 3115 support rotating motor 3116 conductive support holder 3121 high-frequency power supply 3201 transfer caster 3202 reaction vessel support base 3203 exhaust valve connection gate valve 400 photoconductor 401 conductive support 402 Photosensitive layer 403 Photoconductive layer 404 Surface layer 405 Charge injection blocking layer 410 Free surface 411 Charge transport layer 412 Charge generation layer 413 Upper charge injection blocking layer 701 Cleaning blade 702 Control means 703 Toner pool 704 Magnet roller 705-1 Doctor roller 705 2 Restriction blade 705-3 Collection blade 706 Cleaning blade holder 707 Discard path 708 Collection path 709 Collection path opening / closing valve

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/01 G03G 15/01 113Z 2H200 113 114A 114 15/08 503A 15/08 503 15/16 507 9 / 08 101 15/16 15/08 507L 21/10 507D 21/00 326 316 (72) Inventor Hironori Owaki 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) in Canon Inc. 2H005 AA08 AA15 AA21 CB13 EA05 EA10 FA01 FA06 2H030 AA04 AC07 AD03 BB42 2H068 CA03 DA12 DA17 DA23 FA30 FB11 FC11 2H077 AA37 EA13 EA14 2H134 GA01 GB02 HC00 JA11 KA07 2H200 FA14 GA18 GA23 GA44 GA46 GA47 JC02 JC03 KA07

Claims (36)

[Claims] 1. A photoconductor having a photoconductive layer containing at least amorphous silicon formed on a conductive support, and a latent image formed on the photoconductor is developed by a plurality of developing means containing toners of different colors. Developing to form a toner image,
The formed toner image is transferred from the photoconductor to the transfer material by the transfer unit, and the transfer residual toner on the photoconductor after the toner image is transferred is removed from the photoconductor by the cleaning unit. In an electrophotographic method for outputting a full-color image using a magnetic toner as a black toner and a non-magnetic toner as a toner of another color, the non-magnetic toner includes toner particles containing at least a binder resin and a colorant, and inorganic fine powder. And a spherical non-magnetic toner having an average circularity of 0.960 or more. 2. The electrophotographic method according to claim 1, wherein the photoconductor has a surface layer, and the surface layer is a surface layer containing amorphous carbon. 3. The electrophotographic method according to claim 1, wherein the photoconductor has a surface layer, and the surface layer is an amorphous carbon layer. 4. The electrophotographic method according to claim 1, wherein the surface free energy of the outermost surface of the surface layer is 35 to 65 mN / m. 5. The electrophotographic method according to claim 1, wherein the outermost surface of the surface layer has a surface free energy of 40 to 60 mN / m. 6. The non-magnetic toner has an average circularity of 0.3.
2. The value of 970 to 0.995.
6. The electrophotographic method according to any one of claims 1 to 5. 7. The non-magnetic toner according to claim 1, wherein the weight-average particle diameter is 5 to 9 μm, and the number% of particles having a particle diameter of 3.2 μm or less is 10% or less.
The electrophotographic method according to any one of the above. 8. The magnetic toner has a circularity of 0.900.
The electrophotographic method according to any one of claims 1 to 7, wherein the number% of less than 0.970 is 80% or more. 9. The image forming apparatus according to claim 1, wherein the transfer material is an intermediate transfer member, and the toner image superimposed on the intermediate transfer member is transferred to a recording material and output. Electrophotography method. 10. The electrophotographic method according to claim 9, wherein the intermediate transfer member is an endless transfer belt. 11. The electrophotographic method according to claim 9, wherein said intermediate transfer member is a transfer drum. 12. The electrophotographic method according to claim 1, wherein the black toner developing unit is a unit using a magnetic one-component developing method. 13. The electrophotographic method according to claim 1, wherein the developing means of the non-magnetic toner is a means utilizing a two-component developing method. 14. The method according to claim 1, wherein the magnetic toner is separated and collected from the transfer residual toner, and the collected magnetic toner is transported to a developing unit for the black toner and reused for development. The electrophotographic method according to claim 1. 15. The electrophotographic method according to claim 14, wherein a magnet is used as said magnetic toner collecting means. 16. The black toner according to claim 14, wherein the collected magnetic toner is mixed with a replenishment toner in a toner hopper before being supplied to a developer container of a developing unit of the black toner. Electrophotography method. 17. The electrophotographic method according to claim 14, wherein said cleaning means includes a magnet roller. 18. The electrophotographic method according to claim 14, wherein a document ratio of the magnetic toner in the image is calculated, and collection of the magnetic toner is controlled according to the calculation result. . 19. A photoconductor having at least a conductive support, and a photoconductive layer including amorphous silicon and formed on the conductive support, a charging unit for charging the photoconductor, and charging of the photoconductor. A latent image forming means for forming an electrostatic latent image on a surface, and a black toner for forming a black toner image by containing a magnetic toner as a black toner and developing the electrostatic latent image formed on the photoreceptor with the magnetic toner. Developing means, and a color developing means for storing a non-magnetic toner of each color, which is a color toner of a different color, and developing the electrostatic latent image formed on the photoreceptor with the non-magnetic toner to form a toner image of each color An image forming apparatus comprising: a transfer unit configured to transfer a formed toner image from a photoconductor to a transfer material; and a cleaning unit configured to remove residual toner remaining on the photoconductor after the transfer. Over the toner particles containing at least a binder resin and a colorant, and a fine inorganic powder, an electrophotographic apparatus, wherein the average circularity of from spherical non-magnetic toner is 0.960 or more. 20. The electrophotographic apparatus according to claim 19, wherein said photoconductor has a surface layer, and said surface layer is a surface layer containing amorphous carbon. 21. The electrophotographic apparatus according to claim 19, wherein the photoconductor has a surface layer, and the surface layer is an amorphous carbon layer. 22. The electrophotographic apparatus according to claim 19, wherein the surface free energy of the outermost surface of the surface layer is 35 to 65 mN / m. 23. The electrophotographic apparatus according to claim 19, wherein the surface free energy of the outermost surface of the surface layer is 40 to 60 mN / m. 24. The electrophotographic apparatus according to claim 19, wherein the non-magnetic toner has an average circularity of 0.970 to 0.995. 25. The non-magnetic toner has a weight average particle diameter of 5 to 9 μm and a number% of particle diameter of 3.2 μm or less.
Is not more than 10%.
5. The electrophotographic apparatus according to claim 4. 26. The magnetic toner, wherein the circularity is 0.90.
26. The electrophotographic apparatus according to claim 19, wherein the number% of 0 to less than 0.970 is 80% or more. 27. The image forming apparatus according to claim 19, wherein the transfer material is an intermediate transfer member, and the toner image superimposed on the intermediate transfer member is transferred to a recording material and output. Electrophotographic equipment. 28. The electrophotographic apparatus according to claim 27, wherein said intermediate transfer member is an endless transfer belt. 29. The electrophotographic apparatus according to claim 27, wherein said intermediate transfer member is a transfer drum. 30. The black developing means is a means utilizing a magnetic one-component developing method.
30. The electrophotographic apparatus according to any one of 9 to 29. 31. The color developing device according to claim 19, wherein the developing device uses a two-component developing method.
31. The electrophotographic apparatus according to any one of claims 30 to 30. 32. The apparatus according to claim 19, further comprising a separating and collecting unit for separating and collecting the magnetic toner from the transfer residual toner and conveying the collected magnetic toner to the black developing unit. An electrophotographic apparatus according to claim 1. 33. A magnet member for capturing magnetic toner in the transfer residual toner, a non-magnetic toner regulating member for regulating the non-magnetic toner on the magnet member and removing the non-magnetic toner from the magnet member. A waste path through which the non-magnetic toner removed from the magnet member is guided, a magnetic toner regulating member that regulates the magnetic toner on the magnet member and removes it from the magnet member, and a magnetic toner removed from the magnet member 33. The electrophotographic apparatus according to claim 32, further comprising a collection path to be guided. 34. The electrophotographic apparatus has document ratio calculating means for calculating a document ratio of magnetic toner in an image, and the separating and collecting means sets the collecting path in accordance with a calculation result of the document ratio calculating means. 34. The electrophotographic apparatus according to claim 32, further comprising a recovery path opening / closing valve that freely opens and closes. 35. The electrophotographic apparatus according to claim 33, wherein said magnet member is a magnet roller, and said magnet roller also functions as said cleaning member. 36. The black developing means has a toner hopper containing replenished toner, and the toner conveying means conveys the magnetic toner guided to the collection path to the toner hopper, and collects the collected magnetic toner. 33. The toner and the replenishment toner are mixed in a toner hopper.
36. The electrophotographic apparatus according to any one of items 35 to 35.