JPS63217381A - Developer supplying member and its production - Google Patents

Abstract

PURPOSE:To prevent the deterioration of the image quality due to bias drop, and to improve the toner electrification, the friction-resistance and the carrying characteristics of a developer by forming an amorphous carbon film contg.fluorine provided on a cylinderical substrate in a rugged spotting state by a glow discharge decomposing method in a vacuum atmosphere. CONSTITUTION:The amorphous carbon film contg. fluorine is formed on the cylinderical aluminum substrate 752 by making the inside of a reaction chamber 733 in a coating layer manufacturing apparatus into a high vacuum, and feeding gaseous hydrogen and gaseous tetrafluorocarbon in said reaction chamber, and subjecting to a plasma polymerization reaction. The rugged spotting surface is formed on the substrate by transferring the substrate to an electron beam deposition device and forming a latent image on the substrate and transferring again the obtd. substrate to the coating layer manufacturing device followed by plasma-etching. Since the content of a fluorine atom contg. in the polymerized film is 0.1-35atom.%, the friction-resistance of the titled member to an another member is increased. The deterioration of the image quality due to the bias drop, and the electrode effect of the excess and deficient electrification is prevented, and the carrying characteristics of the developer of the titled member is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a developer donor member, and more particularly to a developer donor member in a developer unit of an electrophotographic copying machine.

Conventionally, in electrophotographic copying methods, such as the Renmachi Carlson method, a latent electrostatic TL is formed on a photoconductor by a charging and exposure process, and then toner and carrier are combined. A two-component developer consisting of or a one-component developer consisting only of toner is held on the circumferential surface of a rotatable developer donor member, and brought into contact with the electrostatic latent image to be visualized as a toner image. process is used.

It is a well-known fact that one of the conventional problems in these developing methods is the so-called fog phenomenon. This is because during the electrostatic latent image forming process, development is performed before the charge on the exposed area on the photoreceptor is completely eliminated, so toner adheres electrostatically due to the residual charge, resulting in the copy becoming smeared overall. This refers to a phenomenon that exhibits a certain state. In order to solve such problems, a developing bias application method is commonly used.

The development bias method is a method in which, during development, a DC voltage or an AC voltage of the same polarity and higher polarity than the residual potential of the exposed area on the photoreceptor is superimposed, and the DC voltage is applied to an electrode provided on the developer supplying member side. At the same time, the photoreceptor that is to be the opposite electrode of this electrode or a conductive support that is one of the components of the photoreceptor is kept grounded to form an electric field between the two, and the exposed portion of the photoreceptor is This is a method of preventing toner from adhering to the exposed area by utilizing the repulsion between the charged polarity of the toner and the applied bias voltage polarity.

The above-mentioned method is related to regular development in which the developing operation is performed using a toner having a charge of the opposite polarity to the electrostatic latent image formed on the photoreceptor, but a toner having a charge of the same polarity as the latent image is used. Even in the case of reversal development, the bias voltage is applied using the same method, although there are differences in polarity, potential amount, etc. This developing bias application method is an effective method for preventing the fogging phenomenon, but on the other hand, it causes new problems.

For example, if electrical leakage occurs between the developer-donating member-side electrode and the photoreceptor-side electrode, a fogging phenomenon may occur due to a reduction in the developing bias. There are several factors that can cause such electrical leakage, but for example, in the case of two-component development, magnetic particles commonly used as developer carriers penetrate the photoreceptor layer, causing conductive particles to pass through the photoreceptor layer. 1 (This phenomenon occurs when the photoreceptor reaches the plate. This phenomenon often occurs when the photoreceptor has low hardness. In particular, organic photoreceptors, which have recently made remarkable progress, are problematic because of their low hardness. Even in the so-called pinhole-like defects that often occur on the photosensitive layer, when the magnetic particles commonly used as a carrier in two-component development come into contact with the conductive substrate of the photoreceptor, the -component During development, this occurs when the electrode on the side of the developer donor member comes into direct contact with the conductive substrate of the photoreceptor.The so-called bias drop based on this phenomenon occurs not only in the area where the leak occurs, but also in the developer when the leak occurs. This affects the entire area where the photoreceptor is in contact with the photoreceptor, so in practical copying machines, band-shaped fog occurs on the image, and even though the leak itself is a phenomenon in a small defective area, it can affect the image quality. Significant damage.

On the other hand, in the case of -component development, it is necessary to charge the toner to a predetermined polarity before development depending on the polarity of the electrostatic latent image and the type of regular development or reversal development. Possible methods include using separate friction charging blades, charging the toner with a corona charger, and charging the toner by bringing a metal blade to which a bias voltage is applied into contact with the toner. It is being However, the triboelectric charging blade method has problems in that it is not suitable for high-speed development because the amount of charge on the toner is insufficient, and that a large number of triboelectric charging blades must be arranged to sufficiently charge the toner. The method using a corona discharger has problems such as the toner scattering due to the action of the electric field during corona charging and the inside of the toner layer not being sufficiently charged. In addition, although the above-mentioned problems are less common in the charge applying method using a metal blade, the developer donor member is made conductive to form a potential difference between the metal blade and the developer donor member, and the toner passing between the metal blade and the developer donor member is charged. Therefore, during development, a phenomenon occurs in which the electrode effect by the developer supplying member is too strong and there is no edge effect. That is, in development using -component toner,
Since the thickness of one layer of toner on the developer donor member is at most 50 μm, an extremely large electrode effect occurs because the electrostatic latent image surface and the surface of the developer donor member approach each other to less than the thickness of the toner layer. There were problems such as poor quality and poor reproducibility of low-density originals.

In order to solve these problems, there is a method of coating the developer donor member with a high resistance layer or a high hardness layer.

That is, by always interposing a constant resistance layer between the photoreceptor and the developer supplying member, it is intended to prevent so-called bias drop, insufficient charge amount, or excessive electrode effect as described above.

For example, Japanese Patent Application Laid-Open No. 51-6730 discloses a high resistance layer formed by alumite treatment on the surface of an endless member, or
A developing method for electrophotographic copying in which a coating layer of silicone resin, urea resin, melamine resin, polyvinyl butyral resin, etc. is provided is disclosed. Also, JP-A-55-4
Japanese Patent No. 6768 discloses an electrostatic latent developing device in which a developer supplying member is provided with a surface layer of about 5 mm made of silicone rubber, neoprene rubber, nitrile rubber, etc. and having a volume resistivity of 10 8 Ωam to 10 15 cm.

However, simply coating the developer donor member with a resin-based high resistance layer or high hardness layer as seen in these disclosures does not
Since the resin-based coating layer has a low coefficient of friction, the developer supplying member cannot maintain its original function of conveying the developer, making it impossible to obtain a suitable image density. Therefore, it is effective to improve the developer carrying performance by forming minute irregularities on the surface of the developer donor member, but there are no conventional methods for applying such microfabrication to these coating layers, and there are no methods for applying such microfabrication to these coating layers. There were no materials that could be used.

In order to solve the above-mentioned problem of bias drop, insufficient charge amount, or excessive electrode effect, the image quality is reduced due to the above-mentioned bias drop, insufficient charge amount, or excessive electrode effect. It is necessary to have a correspondingly high resistance. In addition, this coating layer is made of a material that has low adhesion to the developer and is highly hard, in order to prevent contamination from the developer and scratches caused by contact wear with other parts, which often occur during actual use in copying machines. It is necessary to use Further, this coating layer has no so-called unevenness in resistance value over the entire area of the rIi layer provided on the developer donor member, and furthermore, the so-called phenomenon gap between this coating layer and the photoreceptor is kept constant. In order to keep
The film must be homogeneous and have an even thickness. In general, a developer supplying member having such a coating layer needs to have sufficient developer transport performance. however,
Conventional techniques cannot necessarily satisfy these performances, and a coating layer with higher performance is required.

The present invention aims to solve all of these problems and to provide a developer-donating member having a coating layer made of completely different materials and manufacturing methods from those of the prior art.

In order to determine the "point", the developer donor member of the present invention is coated with a fluorine-containing amorphous carbon film produced by a vacuum glow discharge decomposition method, and this fluorine-containing amorphous carbon film is It is characterized by having speckled irregularities. In general, the method for producing a developer donor member of the present invention includes a step of coating with a fluorine-containing amorphous carbon film produced by a glow discharge decomposition method in a vacuum, and a step of applying an electron beam to the fluorine-containing amorphous carbon film. This method is characterized by comprising the steps of forming a latent image by irradiation and developing the latent image by plasma etching.

Hydrocarbon compounds can be used for producing the fluorine-containing amorphous carbon film in the present invention. The phase state of this hydrocarbon compound does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid or solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is possible.

As the hydrocarbon compound, for example, saturated hydrocarbons, unsaturated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc. are used.

There are many types of hydrocarbon compounds that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and pentadecane. , hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, tocosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, and other normal paraffins, as well as isobutane, isopentane, neopentane, isohexane,
Neohexane, 2,3-dimethylbutane, 2-methylhexane, 3-ethylpentane, 2.2-dimethylpentane, 2,4-dimethylpentane, 3.3-dimethylpentane, tributane, 2-methylhebutane, 3 -Methylhebutane, 2.2-dimethylhexane, 2.2.5-dimethylhexane, 2,2.3-trimethylpentane, 2.
Isoparaffins such as 2,4-trimethylpentane, 2,3°3-trimethylpentane, 2,3,4-)dimethylpentane, isonanone, etc. are used.

Examples of unsaturated hydrocarbons include ethylene, propylene, isobutylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl -Olefins such as 2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-nonene, 1-decene, and allene, methylalene, butadiene, pentadiene, hexadiene, cyclopentadiene, diolefins such as ocimene, allocimene, myrcene, hexatriene, and acetylene,
Methylacetylene, 1-butyne, 2-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1
-nonine, 1-decyne, etc. are used.

Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, Cycloparaffins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cycloolefins such as limonene, tervirun, phelandrene, sylvestrene, thuene, carene, pinene, bornylene, kamphuen, fuenchen , cycloundecane, tricyclene, bisabolene, zingiberene, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarbrene, mirene, and other terpenes, steroids, and the like are used.

Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimentene, pseudocumene, mesitylene, prenitene, indulene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene,
Propylbenzene, cumene 1. styrene, biphenyl,
Terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

The phase state of these hydrocarbon compounds is not necessarily gaseous at normal temperature and pressure, but even if they are liquid or solid, they can be easily melted and vaporized by heating or reduced pressure.
Therefore, the plasma CVD (
Chemica I Vapor Deposit
on) can be used.

In the fluorine-containing amorphous carbon film of the present invention, in addition to the hydrocarbon compound, a fluorine compound can be used to add fluorine atoms into the film. The phase state of this fluorine compound does not necessarily have to be a gas phase at room temperature and pressure; it can be used in either a liquid or solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is. Examples of fluorine compounds include fluorine, hydrogen fluoride, chlorine fluoride, bromine fluoride, iodine fluoride, sulfur fluoride, oxygen fluoride, arsenic fluoride, boron fluoride, silicon fluoride, and ammonium hydrogen fluoride. , potassium hydrogen fluoride, sulfuryl fluoride, selenium fluoride, thionyl fluoride, thiophosphoryl fluoride, nitrogen fluoride, tellurium fluoride, niobium fluoride,
Inorganic compounds such as nitrile fluoride, nitrosyl fluoride, cyanogen fluoride, phosphoryl fluoride, or methyl fluoride, ethyl fluoride, propyl fluoride, butyl fluoride, amyl fluoride, hexyl fluoride, heptyl fluoride , octyl fluoride, nonyl fluoride,
Decyl fluoride, ethylene fluoride, butylene fluoride, butadiene fluoride, acetyl fluoride, vinylidene fluoride, fluorobenzene, fluorostyrene, fluoroform, oxalyl fluoride, carbonyl fluoride, ethylidene fluoride, allyl fluoride, Organic compounds such as chromyl fluoride and cyanogen fluoride are used.

The phase state of these fluorine compounds is not necessarily gaseous at normal temperature and pressure, but even if they are liquid or solid, they can be easily melted and vaporized by heating or reduced pressure, and therefore, the fluorine-containing amorphous carbon in the present invention A conventional method of plasma CVD can be used for the in-vacuum glow discharge decomposition method for producing the film. That is, a compound to be used is selected from among the above-mentioned compounds so that at least carbon atoms and fluorine atoms are contained in the raw material gas, and this raw material gas is subjected to discharge decomposition under reduced pressure to decompose the active molecules contained in the generated plasma atmosphere. Polymerization is produced through a plasma CVD reaction in which sexual or charged species are induced onto a substrate by diffusion, electric force, magnetic force, etc., and deposited as the same phase through a recombination reaction on the substrate.

These compound gases are mixed with a carrier gas such as water, helium, argon, or xenon in order to maintain discharge stability, film formation stability, or gas supply stability in plasma CVD reactions. Is it possible to use it?

In addition, these compound gases may be used, for example, gases containing atoms belonging to Group 1II of the periodic table, gases containing atoms belonging to Group V of the periodic table, etc., in order to adjust the electrical properties of the fluorine-containing amorphous carbon film to be produced.
It can be used in combination with a gas containing atoms belonging to the group, a gas containing an alkali metal atom, or a gas containing a halogen atom.

The thickness of the fluorine-containing amorphous carbon film in the present invention is 1 μm to 2 mm, preferably 10 Ltm to 1 μm at the convex portion.
It is preferable that mm and mm are 100 μm to 500 μm. If the film thickness is less than 1 μm, the required resistance value will not necessarily be ensured, and the wear resistance will decrease, which is not preferable. If the film thickness is thicker than 2 mm, the resistance value will be too high, and it is also unfavorable from the viewpoint of productivity. Moreover, the deposition rate of this fluorine-containing amorphous carbon film is 0.01 μm/
It is preferable to set it to 50 micrometers/minute.

A deposition rate lower than 0.01 μm/min is unfavorable in terms of productivity. If the deposition rate is higher than 50 μm/min, the film-forming properties of the fluorine-containing amorphous carbon film will be lowered, resulting in a so-called rough film and the coverage of the substrate surface will be lowered, which is not preferable. The thickness of this fluorine-containing amorphous carbon film can be easily controlled by adjusting the film formation time. The deposition rate of this fluorine-containing amorphous carbon film has different control amounts depending on the type of plasma CVD equipment used, but in order to increase the deposition rate, for example, increasing the flow rate of the organic compound, applying This can be easily controlled by increasing the power, lowering the frequency of applied power, lowering the substrate temperature, or a combination of these methods.

Further, the amount of fluorine atoms contained in the fluorine-containing amorphous carbon film in the present invention is 0.1 to 35 at%, preferably 2
The content is preferably 10 to 25 atomic %, most preferably 10 to 25 atomic %. If the fluorine atom content is less than 0.1 atomic %, it is unfavorable from the viewpoint of durability because it tends to be contaminated by developer or scratches due to contact wear with other members.

If the content of fluorine atoms is more than 35 at %, the amount of charge in the one-component development mentioned above will decrease, which is not preferable.

Further, the shape of the developer supplying member in the present invention is not particularly limited in terms of manufacturing method or practicality, and may have, for example, a cylindrical shape or a belt shape.

The speckled irregularities provided on the fluorine-containing amorphous carbon film in the present invention are obtained by irradiating an electron beam onto the fluorine-containing amorphous carbon film obtained by plasma polymerizing at least one of the raw material gases by glow discharge in a vacuum. It is formed by a step of forming a spot-like latent image by etching, and a step of developing the spot-like latent image by plasma etching.

The shape of the spotty latent image is not particularly limited as long as it satisfies the developer transport performance, but for example, it may be circular,
It can have an elliptical shape, a rectangular shape, etc.

The fluorine-containing amorphous carbon film according to the present invention has a so-called negative etching characteristic in which the electron beam irradiated area becomes a concave part by plasma etching by electron beam writing.
It is also possible to change the etching characteristics to positive type by performing carbon fluoride plasma irradiation after film formation. The carbon tetrafluoride plasma irradiation treatment time needs to be adjusted depending on the plasma conditions and the thickness of the fluorine-containing amorphous carbon film, but approximately 1 minute to 30 minutes is appropriate. Further, carbon tetrafluoride plasma irradiation can be performed using the plasma CVD apparatus used for producing the fluorine-containing amorphous carbon film as is.

The effect of negative/positive reversal due to carbon tetrafluoride plasma irradiation on this fluorine-containing amorphous carbon film is that fluorine atoms are taken into the fluorine-containing amorphous carbon film by the carbon tetrafluoride plasma, or This is thought to be due to carbon tetrafluoride plasma causing atoms in stainless steel members commonly used in vacuum equipment to adhere to the surface of the fluorine-containing amorphous carbon film by sputtering.

In the method for forming speckled irregularities in a fluorine-containing amorphous carbon film according to the present invention, a conventional electron beam lithography method, such as a vector scan method or a raster scan method, is used in the latent image forming step.

For example, a point electron beam, a fixed shaped electron beam, or a variable shaped electron beam can be used as the electron beam. In addition, the development step in the present invention includes
Dry etching using plasma is used.

As described above, in the present invention, it is possible to form any speckled latent image pattern on a fluorine-containing amorphous carbon film without using any wet process.

The depth of the speckled unevenness produced in this way varies depending on the type of developing device in which the developer donor member of the present invention is used, but The film thickness of the fluorine-containing amorphous carbon film in the recessed portion is approximately 0 to 95 mm.
% is preferable. Here, what 0% means is:
The method of completely removing the fluorine-containing amorphous carbon film in the recessed portions by etching is one form of the present invention. Further, the maximum diameter of the spotted unevenness varies depending on the type of developing device in which the developer supplying member of the present invention is used, but it is preferably about 5 μm to 2 mm in both the concave and convex portions.

Next, the present invention will be explained with reference to the drawings. Here, a cylindrical shape will be used as the shape of the developer donor member in the present invention, but the developer donor member in the present invention can be obtained in the same manner with other shapes.

FIG. 1(a) shows a cross-sectional view of the developer supply member according to the present invention, in which (1) is the developer supply member, (2) is the conductive cylindrical member that can serve as a bias application electrode, and (3) is a coating layer made of a fluorine-containing amorphous carbon film. FIGS. 1(b) and 1(c) are side views of the developer supplying member of the present invention, showing examples of speckled irregularities provided on the coating layer.

FIG. 2 shows an example of a two-component developing device equipped with a developer supplying member according to the present invention, and (11) in the figure shows a developing device,
(12) is a developer supplying member, (13) is a developer, (1
4) is a bias application power supply.

The toner in the developer (13) is triboelectrically charged by being mixed and stirred with the carrier, and the toner forms a magnetic brush together with the carrier by magnetic force on the developer supplying member (12) containing a built-in magnet. By the rotation (12), it is moved to the surface facing the photoreceptor (development area).

FIG. 3 shows an example of a one-component developing device equipped with a developer supplying member according to the present invention, and in the figure (21) is a developing device,
(22) is a developer supplying member, (23) is a developer, (24)
) is a bias applying power source, and (25) is a regulating member.

The developer (23) moves with the rotation of the developer supply member (22), and is moved between the regulating member (25) and the developer supply member (22).
Frictional electrification occurs when the material passes through the gap between the material and the material against the pressing force of the regulating member (25). At the same time, the developer supply member (
22) A thin layer of toner is formed on the toner and transferred to the surface facing the photoreceptor (development area).

FIG. 4 shows a plasma CVD apparatus for forming fluorine-containing amorphous carbon poisoning according to the present invention. This device can also be used for dry etching. In the figure, (701) to (706) are the first to sixth tanks in which the raw material compound, bombarded gas, etching gas, and carrier gas, which are in a gaseous state at room temperature, are sealed, and each tank is used for the first to sixth adjustment. It is connected to valves (707) to (712) and first to sixth flow rate controllers (713) to (718). In the figure, (719) to (721) are first to third containers filled with raw material compounds that are in a liquid or solid phase at room temperature, and each container is connected to a first to third temperature controller (722) for vaporization. ) to (724), and each container can be heated by the seventh to ninth control valves (725) to (724).
727) and seventh to ninth flow rate controllers (728) to (7
30). These gases are mixed in a mixer (73
After being mixed in step 1), the reaction chamber (
733). The pipes along the way can be heated by appropriately placed pipe heaters (734) so that the gas, which is the vaporized raw material compound that is in a liquid or solid state at room temperature, does not condense on the way. . A ground electrode (735) and a power application electrode (736) are installed facing each other in the reaction chamber, and each electrode can be heated by an electrode heater (737). The power application electrode (736) is connected to a high frequency power source (739) via a high frequency power matching box (738), a low frequency power source (741) via a low frequency power matching box (740), and a low pass filter (742). A DC power supply (743) is connected through the power supply, and power with different frequencies can be applied by a connection selection switch (744). The pressure inside the reaction chamber (733) can be adjusted by a pressure control valve (745), and the pressure inside the reaction chamber (733) can be reduced through an exhaust system selection valve (746), a diffusion pump (747), and an oil rotary valve. pump (748), or
This is carried out using a cooling exclusion device (749), a mechanical booster pump (750), and an oil rotary pump (748). Regarding exhaust gas, use a suitable exclusion device (753
) after making it safe and harmless, it is exhausted into the atmosphere. These exhaust system piping can also be heated by appropriately placed piping heaters (734) to prevent the vaporized gas of the raw material compound, which is in a liquid or solid phase state at room temperature, from condensing on the way. ing. The reaction chamber (733) can also be heated by the reaction chamber heater (751) for the same reason, and inside thereof, a conductive cylindrical member that also serves as a ground electrode (735) is installed as a substrate (752). , an electrode heater (737) is arranged inside. Substrate (752)
Around the same cylindrical power application electrode (736)
is arranged, and an electrode heater (737) is arranged on the outside. The board (752) is connected to the drive motor (754) from the outside.
It is possible to rotate using.

The plasma CVD apparatus for forming a fluorine-containing amorphous carbon film according to the present invention shown in FIG. By doing so, it is possible to form speckled irregularities on the fluorine-containing amorphous carbon film on the substrate without breaking the vacuum at all.

In the plasma CVD apparatus for forming a fluorine-containing amorphous carbon film according to the present invention shown in FIG. 4, the reaction chamber is heated to 10-4 to 10=T in advance by a diffusion pump.

The pressure is reduced to approximately rr, the degree of vacuum is confirmed, and the gas adsorbed inside the device is desorbed. At the same time, the electrode and substrate are heated to a predetermined temperature using an electrode heater. Then the first
The raw material gases are introduced into the reaction chamber from the sixth to sixth tanks and the first to third containers while being kept at a constant flow using the first to ninth flow rate controllers, and the pressure control valve is used to maintain a constant reduced pressure in the reaction chamber. Keep it. After the gas flow rate is stabilized, the connection selection switch selects, for example, a low frequency power source, and low frequency power is applied to the power application electrode. A discharge is started between the two electrodes, and over time a solid phase fluorine-containing amorphous carbon film is formed on the substrate. The film thickness is controlled by the reaction time, and when a predetermined film thickness and laminated structure are reached, the discharge is stopped to obtain the developer donor member of the present invention. Next, the first to ninth control valves are closed to sufficiently exhaust the inside of the reaction chamber.

The obtained fluorine-containing amorphous carbon film is subjected to the next electron beam lithography process as a fluorine-containing amorphous carbon film having negative etching characteristics according to the third aspect of the present invention. Here, if positive etching characteristics are required in the electron beam lithography process, the same procedure as in the formation of the fluorine-containing amorphous carbon film is performed again to remove any one of the first to sixth tanks into the reaction chamber. What is necessary is to introduce carbon fluoride gas and perform discharge.

As described above, one of the features of the fluorine-containing amorphous carbon film of the present invention is that it is possible to select a negative type or a positive type of etching property with a few operations.

Next, the substrate on which the fluorine-containing amorphous carbon film of the present invention is formed is transferred to an electron beam irradiation device, and a desired spot pattern is drawn by a conventional method to form a latent image.

Next, the substrate on which the latent image has been formed is again transferred to the plasma CVD apparatus for forming a fluorine-containing amorphous carbon film according to the present invention shown in FIG. By the operation described above, an etching gas is introduced into the reaction chamber from any one of the first to sixth tanks, and a discharge is performed to perform development.

By using these series of methods for forming a developer donor member according to the present invention, the developer donor member of the present invention coated with a fluorine-containing amorphous carbon film having speckled irregularities can be easily obtained without using any wet process. Can be done.

The present invention will be explained in detail below.

Step 1 Using a plasma CVD apparatus for forming a fluorine-containing amorphous carbon film, a developer donor member shown in FIG. 1 was produced. As the spotted irregularities, a so-called circular pattern was used for the recesses.

Plasma CV for forming fluorine-containing amorphous carbon film shown in Figure 4
In apparatus D, first, the inside of the reaction chamber (733) is heated to 10
After creating a high vacuum of about -6 Torr, the seventh control valve (72
5) was released, and styrene gas was allowed to flow into the seventh flow rate controller (728) from the first container (719) at a first temperature controller (722) temperature of 65°C. At the same time, the first and second control valves (707 and 708) are released, and the first and second control valves (707 and 708) are opened.
Do not allow hydrogen gas and carbon tetrafluoride gas to flow into the first and second flow rate controllers (713 and 714) from the tanks (701 and 702). Then, adjust the scale of the flow rate controller to set the flow rate of styrene gas to 16.8 sccrrb, the flow rate of hydrogen gas to 1001005c, and the flow rate of carbon tetrafluoride gas to 50 s e cm. The liquid then flowed into the reaction chamber (733). After the flow rate stabilized, the pressure inside the reaction chamber (733) decreased to 0.2T.
The pressure control valve (745) was adjusted so that the

On the other hand, the substrate (752) has a diameter of 22 mm and a length of 330 mm.
A cylindrical aluminum substrate (mm) was preheated to 70°C, and with the gas flow rate and pressure stable, the low frequency power supply (741) connected in advance using the connection selection switch (744) was turned on. , power application type fM (73
6), a power of 145 Watts was applied at a frequency of 50 KHz to perform a plasma polymerization reaction for about 60 minutes, and the substrate (
752) A 200 μm thick fluorine-containing amorphous carbon film was formed thereon. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Elemental analysis was performed on the fluorine-containing amorphous carbon film obtained as described above, and the amount of hydrogen atoms contained in the total constituent atoms was 39 at%, and the amount of fluorine atoms was 10.3.
It was atomic%. Further, when the pencil hardness was measured in accordance with the JIS-5400 standard, it was found to have a hardness of 7H or more, which is much higher than that of a polymer film obtained by a normal organic synthesis reaction.

Next, the cylindrical substrate on which the fluorine-containing amorphous carbon film was formed was placed in an electron beam evaporator (JEB) through a gate valve.
E-48No. 41006 (manufactured by JEOL Ltd.), the electron beam was focused at 100 μm, and while scanning in the longitudinal direction of the cylindrical substrate, the cylindrical substrate was rotated by 30 μm in the circumferential direction for each scan. Formation was carried out.

Here, scanning in the longitudinal direction was stopped every 300 μm, and irradiation with the electron beam was performed while the scanning was stopped. At this time, the degree of vacuum was set to 2.6×10=Torr or less. Electron beam irradiation was performed until the electron irradiation amount reached 1 mr/cm2. Next, the substrate was again transferred to the plasma CVD apparatus for forming a fluorine-containing amorphous carbon film shown in FIG.
Oxygen gas was introduced as an etching gas into the C1 reaction chamber (733) from the sixth tank C706'), and high frequency power with a frequency of 13.56 MHz was applied from the high frequency power source (739) to the power application electrode (736) to generate 50 W. 10 with the power of
Plasma etching was performed for 1 minute and development was performed. The surface of the obtained developer and '3 material was measured using a surface roughness meter (Surfcom 5).
5OA Tokyo Seimitsu Bag), the film thickness of the convex portion was 100 μm, the maximum diameter of the concave portion was approximately 100 μm, and the difference in film thickness between the concave portion and the convex portion was approximately 18 μm.

In order to evaluate the performance of the obtained developer donor member, an EP470Z C Mi) equipped with a two-component developing device as shown in FIG. 2 and equipped with the developer donor member obtained in Example 1 was used.
An evaluation of the so-called bias drop was performed using a commonly used Carlson process using TA Co., Ltd. The photoreceptor used was an n-containing photoreceptor in which a pinhole was intentionally provided in the photosensitive layer to expose the substrate in that area, and regular development was used as the development method.

First, the surface of the photoreceptor was heated to -700V using a common corona discharge.
After the photoreceptor was charged, the entire surface of the photoreceptor was exposed to light, and the surface potential was attenuated to -50V. Next, a developing device equipped with the developer supplying member obtained in Example 1 was applied with a voltage of -150V.
After developing the surface of the photoreceptor while applying a bias potential of , the toner image was transferred onto transfer paper and fixed. After the photoreceptor was neutralized and cleaned, this process was repeated 1000 times.

During this actual copying evaluation, no toner image was formed on the transfer paper according to the potential setting, and no band-shaped fog due to so-called bias drop appeared. However, when a similar evaluation was performed on a developer donor member not provided with a fluorine-containing amorphous carbon film, band-shaped fogging occurred. From this, it can be seen that the developer supplying member according to the first embodiment has a so-called bias f! It was confirmed that it effectively prevents damage.

Next, the bias potential was changed to -450 V, and a live evaluation filli was repeated 1000 times in reversal development. During this actual evaluation, a so-called solid black image was formed on the transfer paper in accordance with the above-mentioned potential setting, and no so-called band-like white spots corresponding to fog in regular development did not appear. However, when a similar evaluation was performed on a developer donor member not provided with a fluorine-containing amorphous carbon film, band-like white spots occurred. From this, it was confirmed that the developer supply member according to Example 1 effectively prevents so-called bias drop.

In order to evaluate the performance of the obtained developer donor member, a single component developing device as shown in FIG. We conducted a test regarding. First, a predetermined toner was placed in the -component developing device, and the developer supplying member obtained in Example 1 was rotated at 1100 rpm for 5 seconds. After the rotation is complete,
When the charge amount of the toner adhering to this developer donor member was determined, a charge amount of 18 μC/g was obtained. However, when a similar evaluation was performed on a developer donor member not provided with a fluorine-containing amorphous carbon film, a charge amount of only 7 μC/g was obtained. From this, it is clear that the developer supplying member according to Example 1 can suitably charge the component-containing toner. @'It has been certified.

In order to evaluate the performance of the obtained developer-donating member, a two-component developing device as shown in FIG. 2 equipped with the developer-donating member obtained in Example 1 was used. A printing durability test was conducted. After a durability test of 30,000 sheets of A4 paper, the surface of the developer donor member was observed and found that there was no peeling of the fluorine-containing amorphous carbon film, and no toner adhesion or scratches were observed. . However, when a similar evaluation was performed on a developer donor member not provided with a fluorine-containing amorphous carbon film, it was found that toner adhered in a so-called filming manner and image density decreased due to decreased toner transportability. From this, it was confirmed that the developer supplying member according to Example 1 had excellent printing durability.

Also, during the above test, the image density of the solid black area was 1°1 to 1.
．． It was 4. However, when similar tests were conducted on a developer donor member provided with a fluorine-containing amorphous carbon film but without speckled irregularities, the image density of the solid black area was 0.8 to 1.0, and the developer transport performance was A decrease in image density was observed due to the low image density. From this, it was confirmed that the developer supplying member according to Example 1 had excellent developer transport performance.

A developer donor member shown in FIG. 1 was prepared using a plasma CVD apparatus for forming a fluorine-containing amorphous carbon film. As the spotted unevenness, a so-called circular pattern was used for the convex portion.

Plasma CV for forming fluorine-containing amorphous carbon film shown in Figure 4
In apparatus D, first, the inside of the reaction chamber (733) is heated to 10
After creating a high vacuum of approximately -6 Torr, the first, second, and third control valves are released, and hydrogen gas is supplied from the first tank (701), butadiene gas is supplied from the second tank (702), and the third tank is supplied with hydrogen gas. (703), carbon tetrafluoride gas is first added.
, second, and third flow rate controllers (713, 714, and 715). Then, adjust the scale of the flow rate controller to set the flow rate of hydrogen gas to 300 seconds, the flow rate of butadiene gas to 60 sccm, and the flow rate of carbon tetrafluoride gas to 120 seconds.
It flowed into the reaction chamber (733) from the main pipe (732). After the flow rate stabilizes, the pressure inside the reaction chamber (733) becomes 1.0.
The pressure control valve (745) was adjusted so that the pressure was Torr. On the other hand, the substrate (752) has a diameter of 22 x a length of 33 mm.
Preheated to 200℃ using a 0mm cylindrical aluminum substrate.
When the gas flow rate and pressure are stable, turn on the low frequency power supply (741) that has been connected in advance using the connection selection switch (744), and connect the power application electrode (73).
6) was applied with a power of 160 Watts at a frequency of 200 KHz to carry out a plasma polymerization reaction for about 2 hours, and the substrate (
752) A fluorine-containing amorphous carbon film having a thickness of 1 mm was formed thereon. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Elemental analysis of the fluorine-containing amorphous carbon film obtained as above revealed that the amount of hydrogen atoms contained was 42 at% and the amount of fluorine atoms was 2.5 at% with respect to all constituent atoms. Met. Further, when the pencil hardness was measured in accordance with the -JIS-5400 standard, it was found to have a hardness of 7H or more, which is much higher than that of a polymer film obtained by a normal organic synthesis reaction.

Next, the fourth control valve (710) is released and the fourth tank (
704) to the fourth flow rate controller (716).
). Then, adjust the scale of the flow rate controller to set the flow rate of carbon tetrafluoride gas to 3Osccm. (732) into the reaction chamber (733). After the flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 1.0 Torr. While keeping the substrate temperature at 130°C and the gas flow rate and pressure stable, press the connection selection switch (744) in advance.
Turn on the high frequency power supply (739) connected by
After applying 150 Watt power to the power application electrode (736) at a frequency of 13.56 MHz and performing plasma treatment for negative/positive reversal for about 1 minute, power application was stopped, the control valve was closed, and the reaction chamber ( 733) was sufficiently evacuated.

Next, the cylindrical substrate on which the fluorine-containing amorphous carbon film was formed was placed in an electron beam evaporator (JE) through a gate valve.
BE-48No, 41006 manufactured by JEOL Ltd.), focused the electron beam at 200 μm, rotated the cylindrical substrate, and focused the electron beam at 500 μm per rotation of the substrate.
A latent image was formed while scanning in the longitudinal direction of the substrate at a rate of .mu.m.

Here, the substrate rotation is stopped every 500 μm in the circumferential direction,
Electron beam irradiation was performed in a stopped state.

At this time, the degree of vacuum was set to 2.6×10 −5 Torr or less. Electron beam irradiation was performed until the electron irradiation amount reached 1 mC/cm2. Next, the substrate was again transferred to the plasma CVD apparatus for forming the fluorine-containing amorphous carbon film shown in FIG. 4 via the gate valve, and the reaction chamber (733 ) in the 6th tank (70
6) Oxygen gas was introduced as an etching gas, and high frequency power with a frequency of 13.56 MHz was applied from a high frequency power source (739) to the power application electrode (736), and plasma etching was performed for 20 minutes with a power of 200 W for development. When the surface of the obtained developer donor member was measured using a surface roughness meter (Surfcom 550A manufactured by Tokyo Seimitsu), the film thickness of the convex portion was approximately 500 μm, the maximum diameter of the concave portion was approximately 200 μm, and the thickness of the convex portion was approximately 500 μm. The difference in film thickness was about 100 μm.

When the performance of the obtained developer donor member was evaluated in the same manner as in Example 1, a slight decrease in charging performance was observed at 14 μC/g in the test regarding the amount of charge using the -component developing device, but other tests were conducted. Almost the same results as Example 1 were obtained. From this, it was confirmed that the developer supplying member according to Example 2 was excellent in so-called bias drop, toner charging property, printing durability, and developer transport performance.

The developer supplying member of the present invention can solve the problem of image quality reduction due to bias drop, insufficient charge amount, or excessive electrode effect, and is also excellent in printing durability and developer transportability.

2 and 3 are drawings showing an example of a developing device equipped with a developer supplying member according to the present invention, and FIG. 4 is a drawing showing a plasma for forming a fluorine-containing amorphous carbon film according to the present invention. It is a drawing showing a CVD apparatus.

Applicant: Minolta Camera Co., Ltd. Figure 2 l Figure 3 I

Claims (3)

[Claims] (1) A developer donor member coated with a fluorine-containing amorphous carbon film produced by a vacuum glow discharge decomposition method, and characterized in that the fluorine-containing amorphous carbon film has speckled irregularities. (2) The developer supplying member according to claim 1, wherein the fluorine-containing amorphous carbon film is subjected to carbon tetrafluoride plasma irradiation treatment. (3) A step of coating with a fluorine-containing amorphous carbon film produced by a vacuum glow discharge decomposition method, a step of irradiating the fluorine-containing amorphous carbon film with an electron beam to form a latent image, and A method for manufacturing a developer donor member, comprising the step of developing the latent image by plasma etching.