JP2009024224A - Carbon film forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbon film forming method by which a high quality carbon film having excellent adhesion to a base material, surface smoothness and low friction properties is formed by suppressing the generation of fine powder by a simple process. <P>SOLUTION: The carbon film forming method includes a process for introducing a discharge gas into a discharge space under atmospheric pressure or a pressure close to the atmospheric pressure to excite the gas, a process for forming a secondary excited gas by mixing the excited discharge gas with a raw material gas introduced horizontally to a base material and containing carbon in the vicinity of the base material on the outside of the discharge space; and a process for forming a carbon film on the base material by exposing the base material to the secondary excited gas. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a carbon film forming method excellent in adhesion to a substrate, surface roughness characteristics, friction characteristics and smoothness.

  In recent years, methods for applying functional films to the surface of substrates have been developed for the purpose of imparting strength, wear resistance, frictional resistance reduction, chemical stability, and oxygen and moisture shielding properties to various substrates. .

  As one of functional films having these characteristics, a carbon film (hard carbon film) has attracted attention. Examples of the carbon film include an amorphous carbon film, a hydrogenated amorphous carbon film, a tetrahedral amorphous carbon film, a nitrogen-containing amorphous carbon film, a metal-containing amorphous carbon film, and the like. (DLC) film. This diamond-like carbon film is also called i-carbon film, amorphous carbon film or hard carbon film, has a very smooth surface, excellent mechanical, electrical and chemical properties, and Because it can be deposited at low temperatures, it is attracting attention as a highly functional film.

  On the other hand, in an image forming apparatus applied to a copying machine, a printer, a facsimile, etc. using an electrophotographic system, a toner image is primarily transferred from a first toner image carrier, and the transferred toner image is carried. An image forming apparatus having an intermediate transfer member that secondarily transfers a toner image onto a recording sheet or the like is known.

  As such an intermediate transfer member, Japanese Patent Application Laid-Open No. 9-212004 discloses that the surface of the intermediate transfer member is coated with silicon oxide, aluminum oxide or the like to improve the releasability of the toner image and to record paper or the like. There are proposals for improving the transfer efficiency.

  However, it is almost impossible for an image forming apparatus having an intermediate transfer body to transfer a toner image at the time of secondary transfer at the present time. For example, cleaning is performed by scraping off toner remaining on the intermediate transfer body from the intermediate transfer body with a blade. I need a device.

  The intermediate transfer member described in the above patent document has a problem that the toner transfer rate at the time of secondary transfer is not sufficient and the durability is not sufficient, and silicon oxide is deposited by vapor deposition, and aluminum oxide or the like is formed by sputtering. Therefore, there is a problem that a large facility such as a vacuum apparatus is required.

  As a method for forming a carbon film on the substrate surface as described above, a known thinning method such as a vacuum deposition method, a sputtering method, a plasma CDV method, or the like is known. For example, a method of forming an amorphous carbon thin film using a vacuum parallel plate type high-frequency plasma CVD apparatus is disclosed (for example, see Patent Document 1). However, the method described in Patent Document 1 has a very low production efficiency because the deposition rate of the carbon film is low and a special large-scale apparatus such as a vacuum apparatus is required. In contrast, a method for forming a carbon film under atmospheric pressure conditions instead of a vacuum apparatus has been studied. For example, a method of forming a hydrocarbon compound film (DLC) on the outer surface or inner surface of a plastic bottle using an atmospheric pressure low temperature plasma method is disclosed (for example, refer to Patent Document 2). However, in the method described in Patent Document 2, an expensive helium gas is used as the discharge gas, and it is difficult to say that the adhesion to the substrate is sufficient. In addition, a method of forming a hard carbon film on a silicon wafer by a torch method under atmospheric pressure conditions (for example, see Non-Patent Document 1). However, the method described in Non-Patent Document 1 is difficult to apply to film formation using a resin film or the like having a problem in heat resistance because the substrate temperature at the time of carbon film formation is high. The film forming speed is low, the area that can be formed once is small, and expensive helium or the like is used as a discharge gas, so that the production efficiency is low.

  Further, an excitation gas is formed by a discharge gas and a raw material gas in a discharge space that is applied between opposing electrodes under atmospheric pressure conditions and is cut off from the atmosphere, and the excitation gas is exposed to the substrate outside the discharge space. A method of forming a hard carbon film or the like is disclosed (for example, see Patent Document 3). According to this method, it is said that a homogeneous thin film can be formed by eliminating the influence of the atmosphere during film formation, particularly the influence of impurities such as oxygen on the formed film. However, in the method described in Patent Document 3, since a raw material gas containing a thin film forming compound is supplied to the discharge space, the thin film forming compound is directly exposed to the discharge space, so that it is difficult to suppress vapor phase growth. As a result, a carbon film containing pinholes was formed by fine powder or the like grown in the discharge space, and vapor phase growth could not be completely suppressed.

In addition, a raw material gas containing a hard carbon film forming material is supplied between the counter electrodes under atmospheric pressure conditions, and a thin film is formed by bringing the base material into the discharge space into the raw material gas excited by plasma discharge. An apparatus for manufacturing a transfer body is disclosed (for example, see Patent Document 4). According to this method, it is possible to obtain an intermediate transfer body having high transferability and excellent cleaning properties and durability, but there are still problems in adhesion and friction properties with the substrate. is the current situation.
JP-A-5-273425 JP 2001-158415 A JP-A-5-44041 International Publication WO2006 / 129543 Specification Japan Journal of Applied Physics Vol. 44, no. 52, 2005, pp. L1573-L1575

  The present invention has been made in view of the above-mentioned problems, and its purpose is to suppress the generation of fine powder by a simple method, and to provide high quality with adhesion to a substrate, surface smoothness, and low friction characteristics. An object of the present invention is to provide a carbon film forming method for forming a carbon film.

  The above object of the present invention is achieved by the following configurations.

  1. A step of introducing a discharge gas into a discharge space and exciting it under atmospheric pressure or a pressure near atmospheric pressure, the excited discharge gas, and a raw material gas containing carbon introduced horizontally to the substrate, A step of mixing in the vicinity of the base material outside the discharge space to form a secondary excitation gas; and a step of forming a carbon film on the base material by exposing the base material to the secondary excitation gas. A carbon film forming method.

  2. 2. The carbon film forming method according to 1 above, wherein the carbon-containing source gas is a gas containing a hydrocarbon or an alcohol.

  3. 3. The carbon film forming method according to 1 or 2, wherein the discharge space is formed by applying a high frequency voltage between opposing electrodes.

  4). 4. The carbon film forming method as described in 3 above, wherein the high-frequency voltage has a frequency of 10 kHz or more and 10 GHz or less.

  5). The discharge gas is 1) nitrogen gas, 2) noble gas, 3) oxygen gas, carbon dioxide gas, chlorine gas, hydrogen gas, and nitrogen gas containing at least one gas selected from metal-containing gas, or 4) oxygen 5. The carbon film forming method according to any one of 1 to 4, wherein the carbon film forming method is a rare gas containing at least one gas selected from gas, carbon dioxide gas, chlorine gas, hydrogen gas, and metal-containing gas. .

  6). 6. The carbon film forming method according to any one of 1 to 5, wherein the base material is a polymer film or a polymer film having a metal-containing thin film as an outermost layer.

  7. 7. The carbon film forming method according to any one of 1 to 6, wherein the carbon-containing source gas contains nitrogen gas or rare gas as a carrier gas.

  8). 4. The carbon film forming method as described in 3 above, wherein the high-frequency voltage has a frequency of 1 GHz or more and 10 GHz or less.

  9. 9. The carbon film forming method according to any one of 1 to 8, wherein the carbon film has a hydrogen atom content of 30 atomic% or more.

  According to the present invention, it is possible to provide a carbon film forming method for forming a high-quality carbon film that suppresses generation of fine powder and has adhesion with a base material, surface smoothness, and low friction characteristics by a simple method. did it.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above-mentioned problems, the present inventors have introduced a step of introducing a discharge gas into a discharge space and exciting it under atmospheric pressure or a pressure near atmospheric pressure, the excited discharge gas, and a substrate. A source gas containing carbon introduced horizontally with respect to the substrate outside the discharge space to form a secondary excitation gas, and exposing the substrate to the secondary excitation gas, A carbon film forming method characterized by comprising a step of forming a carbon film on a substrate, thereby suppressing the generation of fine powder by a simple method, adhesion to the substrate, surface smoothness, It has been found that a carbon film forming method for forming a high-quality carbon film having low friction characteristics can be realized, and the present invention has been achieved.

  As described above, in the carbon film forming method of the present invention, after exciting the discharge gas between the counter electrodes, in this discharge space, without introducing the raw material gas containing carbon, the excited discharge gas, The material gas containing carbon introduced horizontally with respect to the base material is mixed outside the discharge space to form a secondary excitation gas, and the base material is exposed to this secondary excitation gas to make it homogeneous on the base material. This is a method for forming a hard carbon film that is excellent and does not generate pinholes. That is, in the present invention, since the source gas containing carbon is excited by mixing with the excited discharge gas in the region near the substrate (outside the discharge space), the gas phase grows into fine particles or the like in the space region. Since the secondary excitation gas reaches the surface of the substrate before the growth occurs, the generation of fine particle dust can be effectively prevented.

  Details of the present invention will be described below.

  First, an atmospheric pressure plasma processing apparatus applied to the carbon film forming method of the present invention will be described.

  The atmospheric pressure plasma processing apparatus applied to the carbon film forming method of the present invention includes means for introducing a discharge gas into a discharge space and exciting it under atmospheric pressure or a pressure near atmospheric pressure, the excited discharge gas, A source gas containing carbon introduced horizontally with respect to the material is mixed in the vicinity of the substrate outside the discharge space to form a secondary excitation gas, and by exposing the substrate to the secondary excitation gas, And means for forming a carbon film on the substrate.

  In general, methods for forming a functional thin film on a substrate are roughly classified into physical vapor deposition and chemical vapor deposition. Physical vapor deposition is a method of forming a substance in a gas phase. It is a method of depositing a thin film of a target substance (for example, carbon film, etc.) on the surface by a physical method, and as these methods, a vapor deposition (resistance heating method, electron beam vapor deposition, molecular beam epitaxy) method, Examples include ion plating and sputtering. On the other hand, the chemical vapor deposition method is a method in which a raw material gas containing a target thin film component is supplied onto a substrate, and a film is deposited by a chemical reaction on the substrate surface or in the gas phase. For the purpose of activating the plasma, there is a method of generating plasma or the like, and examples thereof include a plasma CVD (chemical vapor deposition) method and an atmospheric pressure plasma CVD method.

  Among them, the present invention is characterized by applying an atmospheric pressure plasma treatment method (hereinafter also referred to as an atmospheric pressure plasma CVD method).

  Compared with the plasma CVD method under vacuum, the atmospheric pressure plasma processing method, which performs plasma CVD processing near atmospheric pressure, does not require a reduced pressure and is not only highly productive, but also has a high plasma density. The film speed is high, and further, under a high pressure condition of atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free path is very short, so that a very homogeneous film can be obtained.

  For example, the carbon film mainly composed of carbon according to the present invention excites a gas containing a source gas containing carbon in a discharge space where a high-frequency electric field is generated under atmospheric pressure or a pressure in the vicinity thereof. It is formed by mixing with a discharge gas to form a secondary excitation gas and exposing the substrate to this secondary excitation gas.

  The atmospheric pressure or the pressure in the vicinity thereof in the present invention is about 20 kPa to 110 kPa, and 93 kPa to 104 kPa is preferable in order to obtain the good effects described in the present invention.

  The excited gas as used in the present invention means that at least a part of the molecules in the gas move from the existing state to a higher state by obtaining energy. Excited gas molecules, radicalized gas molecules A gas containing ionized gas molecules corresponds to this.

  That is, the pressure between the counter electrodes (discharge space) is set to atmospheric pressure or a pressure in the vicinity thereof, a discharge gas is introduced between the counter electrodes, a high-frequency voltage is applied between the counter electrodes, and the discharge gas is brought into a plasma state. The discharge gas in a plasma state and the source gas are mixed outside the discharge space, and the substrate is exposed to this mixed gas (secondary excitation gas) to form a carbon film on the substrate.

  Hereinafter, an atmospheric pressure plasma processing apparatus according to the present invention will be described with reference to the drawings. In addition, although the following description may include assertive expressions for terms and the like, they show preferred examples of the present invention and limit the meaning and technical scope of the terms of the present invention. It is not a thing.

  Conventionally known atmospheric pressure plasma processing apparatuses are roughly classified into the following two systems.

  One method is a so-called plasma jet type atmospheric pressure plasma discharge treatment apparatus, in which a high frequency voltage is applied between counter electrodes, a gas containing a discharge gas is supplied between the counter electrodes, and the mixed gas is converted into plasma. Then, the plasma mixed gas and the raw material gas are combined and mixed, and then sprayed onto the substrate outside the discharge space to form a thin layer.

  The other method is a so-called direct-type atmospheric pressure plasma discharge treatment apparatus. After mixing a mixed gas containing a discharge gas and a raw material gas, the discharge is performed with a transparent substrate supported between opposing electrodes. In this method, the mixed gas is introduced into the space, and a high-frequency voltage is applied between the counter electrodes to form a thin layer on the substrate in the discharge space.

  The atmospheric pressure plasma processing apparatus according to the present invention is basically a method using the former plasma jet type atmospheric pressure plasma processing apparatus.

  Prior to describing the atmospheric pressure plasma processing apparatus according to the present invention, a conventional atmospheric pressure plasma processing in which a mixed gas of a raw material gas and a discharge gas is introduced into a discharge space between opposing electrodes to form an excitation gas in the discharge space. The apparatus will be described.

  FIG. 1 is a schematic view showing an example of a conventional atmospheric pressure plasma processing apparatus that introduces a mixed gas of a source gas and a discharge gas into a discharge space to form an excitation gas in the discharge space.

  The two-frequency jet type atmospheric pressure plasma processing apparatus shown in FIG. 1 is not shown in FIG. 1 except for the plasma discharge processing apparatus and the electric field applying means having two power sources. It is the device which has.

The atmospheric pressure plasma discharge processing apparatus 210 has a counter electrode composed of a first electrode 211 and a second electrode 212, and the frequency from the first power source 221 is provided between the counter electrodes between the counter electrode and the first electrode 211. A _first high-frequency electric field of ω ₁ , electric field strength V ₁ , and current I ₁ is applied, and a second frequency of ω ₂ , electric field strength V ₂ , and current I ₂ from the second power source 222 is applied to the second electrode 212. A high frequency electric field is applied. The first power source 221 can apply a higher frequency electric field strength (V ₁ > V ₂ ) than the second power source 222, and the first frequency ω ₁ of the first power source 221 is higher than the second frequency ω ₂ of the second power source 222. A low frequency can be applied.

  A first filter 223 is installed between the first electrode 211 and the first power source 221, which facilitates the passage of current from the first power source 221 to the first electrode 211, and the current from the second power source 222. Is designed so that the current from the second power source 222 to the first power source 221 is less likely to pass through.

  In addition, a second filter 224 is installed between the second electrode 212 and the second power source 222 to facilitate passage of current from the second power source 222 to the second electrode, and from the first power source 221. It is designed to ground the current and make it difficult to pass the current from the first power source 221 to the second power source 222.

  A mixed gas MG of a discharge gas and a raw material gas containing a raw material compound for forming a thin film is introduced from the gas supply means into the space (discharge space) 213 between the counter electrodes of the first electrode 211 and the second electrode 212, A discharge is generated by applying a high-frequency electric field from the first electrode 211 and the second electrode 212, and the excited mixed gas MG 'in which the mixed gas MG is changed to a plasma state is jetted out to the lower side of the counter electrode (the lower side of the paper). Then, the processing space formed by the lower surface of the counter electrode and the base material F is filled with a plasma gas MG °, and a thin film is formed near the processing position 214 on the base material F conveyed from the previous process. It is. During the formation of the thin film, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means. Depending on the temperature of the substrate during the plasma discharge treatment, the physical properties and composition of the resulting thin film may change, and the temperature is controlled using an insulating material such as distilled water or oil as a temperature control medium. . FIG. 1 shows a measuring instrument used for measuring the high-frequency electric field strength (applied electric field strength) and the discharge starting electric field strength. 225 and 226 are high-frequency voltage probes, and 227 and 228 are oscilloscopes.

  However, a mixed gas MG obtained by mixing a discharge gas and a raw material gas containing a raw material compound containing carbon for forming a carbon film is directly applied in the discharge space between the counter electrodes (in the discharge space) as shown in FIG. Therefore, a certain amount of time is required until the target base material is reached after the mixed gas MG containing the source gas is excited. As a result, in the mixed gas MG ′ excited in the discharge space, fine particles (dust) are generated due to vapor phase growth, and the dust adheres to the surface of the counter electrode, causing discharge failure, or By reaching and depositing on the surface of the substrate, it becomes a factor inducing the occurrence of pinholes and the like.

  In the present invention, as a result of studies to solve the above problems, a step of introducing a discharge gas into a discharge space and exciting it under atmospheric pressure or a pressure near atmospheric pressure, the excited discharge gas, and a substrate A source gas containing carbon introduced horizontally with respect to the substrate outside the discharge space to form a secondary excitation gas, and exposing the substrate to the secondary excitation gas, An atmospheric pressure plasma processing apparatus including a step of forming a carbon film on a substrate is used.

  FIG. 2 is a schematic view showing an example of an atmospheric pressure plasma processing apparatus applicable to the present invention.

  The atmospheric pressure plasma processing apparatus shown in FIG. 2 supplies only the discharge gas to the discharge space formed between the counter electrodes as an excitation gas, while supplying the source gas containing the carbon film forming material in parallel with the base material. The discharge gas excited outside the discharge space and the source gas supplied horizontally are combined and mixed to form a secondary excitation gas, and carbon is obtained by instantly exposing the substrate to the secondary excitation gas. This is a method of forming a film.

  In the atmospheric pressure plasma processing apparatus 2 shown in FIG. 2, a first electrode 3a and a second electrode 3b connected to a power source 4 are arranged at opposed positions. At least one of the electrodes is covered with a dielectric, and a plasma discharge is generated by applying a high frequency voltage from the power source 4 to the discharge space 6 formed between the electrodes.

  By supplying the discharge gas G from the discharge gas supply means 5 to the space (discharge space) 6 between the counter electrodes, the discharge gas G is excited to become the excited discharge gas G ′, and the mixed region with the source gas outside the discharge space Sent to 9.

  On the other hand, the raw material gas M containing the raw material compound for forming the carbon film is supplied from the raw material gas supply means 7 to the raw material gas supply path 8 and sent to the mixing region 9 in a state parallel to the base material F. The gas G ′ and the outside of the discharge space are mixed to form the secondary excitation gas 10. The carbon film 11 is formed on the base material F by exposing the base material F to the secondary excitation gas 10. The waste gas 12 used for forming the carbon film is discharged out of the system via the exhaust gas passage 13.

  As shown in FIG. 2, by supplying the source gas from the parallel direction to the base material F with respect to the excitation discharge gas G ′ supplied in the vertical direction from the upper part to the lower part of the drawing, both gases are uniform in a short time. Thus, a homogeneous hard carbon film can be formed on the substrate F without causing generation of carbon fine particles by vapor phase growth.

  FIG. 3 is a schematic view showing another example of an atmospheric pressure plasma processing apparatus applicable to the present invention.

  The atmospheric pressure plasma processing apparatus described in FIG. 3 is a two-frequency jet type atmospheric pressure plasma processing apparatus similar to that described in FIG.

  In the atmospheric pressure plasma processing apparatus shown in FIG. 3, the first electrode 3a connected to the first power source 21 and the second electrode 3b connected to the second power source 22 are arranged at opposite positions as in FIG. Yes. At least one of the electrodes is covered with a dielectric, and plasma discharge is generated by applying a high frequency voltage from the power sources 21 and 22 to the discharge space 6 formed between the electrodes.

  By supplying the discharge gas G from the discharge gas supply means 5 to the space (discharge space) 6 between the counter electrodes, the discharge gas G is excited to become the excited discharge gas G ′, and the mixed region with the source gas outside the discharge space Sent to 9.

  On the other hand, the raw material gas M containing the raw material compound for forming the carbon film is supplied from the raw material gas supply means 7 to the raw material gas supply path 8 and sent to the mixing region 9 in a state parallel to the base material F. The gas G ′ and the outside of the discharge space are mixed to form the secondary excitation gas 10. The carbon film 11 is formed on the base material F by exposing the base material F to the secondary excitation gas 10. The gas 12 used for forming the carbon film is discharged out of the system via the exhaust gas passage 13.

A first high frequency electric field of frequency ω ₁ , electric field strength V ₁ , and current I ₁ from the first power source 21 is applied to the first electrode 3a provided between the counter electrodes, and the second electrode 3b is supplied with the second high frequency electric field. A second high frequency electric field of frequency ω ₂ , electric field strength V ₂ , and current I ₂ from the power source 22 is applied. The first power source 21 can apply a higher frequency electric field strength (V ₁ > V ₂ ) than the second power source 22, and the first frequency ω ₁ of the first power source 21 is higher than the second frequency ω ₂ of the second power source 22. A low frequency can be applied.

  A first filter 23 is installed between the first electrode 3a and the first power source 21 to facilitate passage of current from the first power source 21 to the first electrode 3a. Is designed so that the current from the second power source 22 to the first power source 21 is less likely to pass through.

  In addition, a second filter 24 is installed between the second electrode 3b and the second power source 22 to facilitate passage of current from the second power source 22 to the second electrode 3b. Is designed so that the current from the first power source 21 to the second power source 22 is difficult to pass. FIG. 3 shows a measuring instrument used for measuring the high-frequency electric field strength (applied electric field strength) and the discharge starting electric field strength. Reference numerals 25 and 26 are high-frequency voltage probes, and reference numerals 27 and 28 are oscilloscopes.

  FIG. 4 is a schematic view showing an example in which the carbon film forming method of the present invention is applied to the production of an electrophotographic intermediate transfer member.

  FIG. 4 is a schematic diagram illustrating an example of an intermediate transfer body manufacturing apparatus that manufactures an intermediate transfer body.

  The intermediate transfer body manufacturing apparatus 102 (plasma jet system in which the discharge space and the carbon film deposition region are different and plasma is jetted onto the base material) forms a hard carbon film on the base material 175, and is an endless belt-shaped intermediate device. It is composed of a roll 120 and a driven roller 201 that are wound around a transfer material base 175 and rotated in the direction of the arrow, and an atmospheric pressure plasma CVD apparatus 103 that is a film forming apparatus for forming a hard carbon film on the surface of the base. Yes.

  The atmospheric pressure plasma processing apparatus 103 is a discharge region in an opposed region between at least one pair of fixed electrodes 121 arranged along the outer periphery of the roll 120, one fixed electrode 121a of the fixed electrode 121, and the other fixed electrode 121b. The discharge space 123 to be performed, the discharge gas supply device 124 for supplying the discharge gas to the discharge space 123, and the source gas installed at the side position of one fixed electrode 121b were excited by the source gas supply device (not shown). A source gas supply path 113 is provided to supply a position where the discharge gas meets. Further, the discharge vessel 129 that reduces the inflow of air into the discharge space 123 and the like, the first power source 125 connected to one fixed electrode 121a, and the second power source 126 connected to the other fixed electrode 121b. And an exhaust part 128 for exhausting the used waste gas G ′.

  A raw material gas supply device (not shown) includes a raw material gas for forming a carbon film, for example, an amorphous carbon film, a hydrogenated amorphous carbon film, a tetrahedral amorphous carbon film, a nitrogen-containing amorphous carbon film, a metal-containing amorphous carbon film, or the like. , And supplied to the mixing position with the excitation discharge gas.

  Further, the driven roller 201 is urged in the direction of the arrow by the tension urging means 202 and applies a predetermined tension to the base material 175. The tension urging means 202 cancels the urging of the tension when the base material 175 is changed, and the base material 175 can be easily changed.

  The first power supply 125 outputs a voltage having a frequency ω1, the second power supply 126 outputs a voltage having a frequency ω2, and the electric field V in which the frequencies ω1 and ω2 are superimposed is generated in the discharge space 123 by these voltages. . Then, the source gas G is turned into plasma by the electric field V, and the excitation source gas and the source gas supplied from the source gas supply path 13 are mixed in a region outside the discharge space below the discharge space 123 to obtain a secondary excitation gas. . A carbon film is formed by exposing the substrate 175 to the secondary excitation gas.

  In addition, in order to improve the adhesion between the carbon film and the base material, a gas supply device for supplying a gas such as argon or oxygen and a fixed electrode are provided upstream of the fixed electrode for forming the carbon film and the mixed gas supply device. Plasma treatment may be performed to activate the surface of the substrate.

  FIG. 5 is a schematic diagram in which a broken line portion (atmospheric pressure plasma processing apparatus 103) of the intermediate transfer body manufacturing apparatus shown in FIG. 4 is extracted.

  FIG. 5 is a schematic view of an atmospheric pressure plasma processing apparatus for producing an intermediate transfer member by an atmospheric pressure plasma discharge method.

  The atmospheric pressure plasma processing apparatus shown in FIG. 5 has substantially the same configuration as the apparatus shown in FIG. 3 described above, although the substrate transport direction is opposite.

  The atmospheric pressure plasma CVD apparatus 104 includes at least one pair of rollers that detachably rolls and rotates the base material F, and at least one pair of electrodes that perform plasma discharge. The one electrode is one of the pair of rollers, the other electrode is a fixed electrode facing the one roller through the base material, and the one roller and the fixed electrode An apparatus for manufacturing an intermediate transfer body in which the base material is exposed to plasma generated in a facing region to deposit and form the hard carbon-containing layer. For example, when nitrogen is used as a discharge gas, a high voltage is applied by one power source. , And by applying a high frequency with the other power source, the discharge is stably started and the discharge is continued.

  As described above, the atmospheric pressure plasma CVD apparatus 104 includes the discharge gas supply device 124, the fixed electrode 121a, the first power source 125, the first filter 125a, the roll electrode 120, and the driving means 120a that drives and rotates the roll electrode in the arrow direction. The second power supply 121b and the second filter 126a are provided, and plasma discharge is performed in the discharge space 111 to excite the discharge gas G, thereby forming the excited discharge gas G2.

  On the other hand, the raw material gas M containing the raw material compound for forming the carbon film is supplied from the raw material gas supply means 127 to the raw material gas supply path 113 and sent to the mixing region 9 in a state parallel to the base material F, and the excited discharge The gas G2 and the outside of the discharge space are mixed to form the secondary excitation gas 112. The carbon film 130 is formed on the substrate F by exposing the substrate F to the secondary excitation gas 112.

A first high-frequency electric field having a frequency ω ₁ , an electric field strength V ₁ and a current I ₁ from the first power source 125 is applied to the first electrode 121a provided between the counter electrodes, and a second high-frequency electric field is applied to the second electrode 121b. A second high frequency electric field of frequency ω ₂ , electric field strength V ₂ , and current I ₂ from the power supply 126 is applied. The first power source 125 can apply a higher frequency electric field strength (V ₁ > V ₂ ) than the second power source 126, and the first frequency ω ₁ of the first power source 125 is higher than the second frequency ω ₂ of the second power source 126. A low frequency can be applied.

  A first filter 125 a is installed between the first electrode 121 a and the first power source 125, which facilitates the passage of current from the first power source 125 to the first electrode 121 a, and the current from the second power source 126. Is designed so that the current from the second power supply 126 to the first power supply 125 does not easily pass.

  In addition, a second filter 126a is installed between the second electrode 121b and the second power supply 126 to facilitate passage of current from the second power supply 126 to the second electrode 121b. Is designed so that the current from the first power supply 125 to the second power supply 126 is difficult to pass.

  Examples of the high-frequency power source that can be used in the atmospheric pressure plasma processing apparatus described in each figure include a high frequency power source (3 kHz) manufactured by Shinko Electric, a high frequency power source (5 kHz) manufactured by Shinko Electric, a high frequency power source (15 kHz) manufactured by Shinko Electric, Electric high frequency power supply (50 kHz), Hayden Laboratory high frequency power supply (continuous mode use, 100 kHz), Pearl Industrial high frequency power supply (200 kHz), Pearl Industrial high frequency power supply (800 kHz), Pearl Industrial high frequency power supply (2 MHz), Japan An electronic high frequency power supply (13.56 MHz), a pearl industrial high frequency power supply (27 MHz), a pearl industrial high frequency power supply (150 MHz), or the like can be used. Alternatively, a power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used. Among them, as a high frequency power source applied in the present invention, a high frequency power source having a frequency of 10 kHz or more and 10 GHz or less is preferably used, and a high frequency power source having a frequency of 1 GHz or more and 10 GHz or less is further preferably used.

In the present invention, for example, in the case of the two-frequency system, the power supplied between the electrodes facing each other from the first and second power sources supplies power (output density) of 1 W / cm ² or more to the fixed electrode 21 and discharges. A gas is excited to generate plasma, and an excited discharge gas is obtained. The upper limit value of the power supplied to the fixed electrode is preferably 50 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called continuous mode and an intermittent oscillation mode called ON / OFF intermittently called pulse mode. Either of them can be used, but the supplied high frequency is the continuous sine wave This is preferable because a denser and better quality film can be obtained.

  It is preferable to use an electrode that can maintain a uniform and stable discharge state by applying a strong electric field as described above to the electrode, and the fixed electrode has at least one electrode surface to withstand discharge by a strong electric field. Is coated with the following dielectric.

  FIG. 6 is a perspective view showing an example of the fixed electrode.

  In FIG. 6A, a rectangular columnar fixed electrode 221 is coated with a ceramic coated dielectric 210d that is sealed with an inorganic material after thermal spraying of ceramic on a conductive base material 210c such as metal. It consists of a combination. Further, as shown in FIG. 6B, the rectangular columnar fixed electrode 221 'is constituted by a combination in which a conductive base material 210A such as metal is coated with a lining dielectric 210B provided with an inorganic material by lining. May be.

  Next, each material used in the carbon film forming method of the present invention using an atmospheric pressure plasma processing apparatus will be described.

(Raw material gas)
In the method for forming a carbon film of the present invention, a gas or liquid organic compound gas, particularly a hydrocarbon gas, is used as a raw material gas for forming the carbon film at room temperature. The phase state of these raw materials does not necessarily need to be a gas phase at normal temperature and normal pressure, and can be a liquid phase or a solid phase as long as it can be vaporized through heating, decompression, etc. through melting, evaporation, sublimation, etc. But it can be used. As for the hydrocarbon gas as the raw material gas, for example, paraffinic hydrocarbons such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ and C ₄ H ₁₀ , and acetylene carbonization such as C ₂ H ₂ and C ₂ H ₄ are used. Gases containing at least all hydrocarbons such as hydrogen, olefinic hydrocarbons, diolefinic hydrocarbons, and aromatic hydrocarbons can be used. Further, other than hydrocarbons, for example, alcohols, ketones, ethers, esters, CO, CO _{2 and the} like can be used as long as they are compounds containing at least a carbon element. In the present invention, hydrocarbons or alcohols are particularly preferable. It is preferable to contain. The source gas preferably contains nitrogen gas or a rare gas as a carrier gas.

  In the present invention, a hard carbon film such as an amorphous carbon film, a hydrogenated amorphous carbon film, a tetrahedral amorphous carbon film, a nitrogen-containing amorphous carbon film, or a metal-containing amorphous carbon film is formed using the source gas. Further, in the carbon film according to the present invention, the hydrogen atom content is preferably 30 atomic% or more.

(Discharge gas)
The discharge gas refers to a gas that is plasma-excited under the conditions applied between the counter electrodes. Examples of the discharge gas that can be preferably applied in the present invention include 1) nitrogen gas, 2) argon, helium, neon, krypton, xenon, and the like. Or 3) nitrogen gas containing at least one gas selected from oxygen gas, carbon dioxide gas, chlorine gas, hydrogen gas and metal-containing gas, 4) oxygen gas, carbon dioxide gas, chlorine gas, hydrogen gas And a rare gas containing at least one gas selected from metal-containing gases. Of these, nitrogen and argon are preferably used.

(Base material)
In the carbon film forming method of the present invention, the substrate for forming the carbon film according to the present invention is not particularly limited, but a polymer film or a polymer film having a metal-containing thin film as the outermost layer is preferable.

  Examples of the polymer film applied to the present invention include polymethyl methacrylate (PMMA), acrylonitrile-butadiene-styrene resin (ABS), ethylene-vinyl acetate resin (EVAC), ethylene-vinyl alcohol resin (EVOH), and polyamide. (PA), polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene (PE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polymethylpentene (PMP), polypropylene ( PP), polystyrene (PS), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), styrene-acrylonitrile resin (SAN), triacetyl cellulose (TAC), cellulose triacete Polymer films such as cellulose esters such as cellulose diacetate, cellulose acetate propionate or cellulose acetate butyrate, polyimide, polyetheretherketone, polyvinylidene fluoride, ethylenetetrafluoroethylene copolymer, polyamide and polyphenylene So-called engineering plastic materials such as sulfide can be used. These polymer films can be added with a conductive agent or the like as required. Carbon black can be used as the conductive agent. Carbon black can be used without particular limitation, and neutral carbon black may be used.

  Moreover, the form which has a metal containing thin film on the polymer film mentioned above may be sufficient. Examples of these metal-containing thin films include thin films composed of metal oxides, metal nitrides, or metal oxynitrides, such as thin films formed of organic metal compounds, halogen metal compounds, metal hydrogen compounds, and the like. Examples thereof include silicon oxide, silicon oxide, aluminum oxide, silicon nitride, silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, and tin oxide.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
《Preparation of carbon film formation sample》
[Preparation of Sample 1]
As a base material, a single-frequency type of a system in which the source gas shown in FIG. 2 is supplied horizontally to an electrode on a polyethylene naphthalate film having a thickness of 100 μm (a film made by Teijin DuPont, hereinafter abbreviated as PEN). Using a plasma jet type atmospheric pressure plasma processing apparatus, a carbon film having a thickness of 200 nm was formed under the following gas conditions and discharge conditions to obtain Sample 1.

<Power supply conditions>
Power supply: High frequency side 27.12 MHz 6 W / cm ²
<Electrode conditions>
The square electrodes of the first electrode 3a and the second electrode 3b were manufactured by subjecting a 30 mm square hollow titanium pipe to ceramic spraying as a dielectric.

Dielectric thickness: 1mm
Electrode width: 300mm
Applied electrode temperature: 90 ° C
Slit gap between electrodes: 1.0mm
<Gas conditions>
Discharge gas: Ar, 100 slm
Source gas: C ₂ H ₂ , 200 sccm
Using the plasma jet type atmospheric pressure plasma processing apparatus 2 shown in FIG. 2, a discharge gas G (Ar gas) is supplied from the discharge gas supply means 5 between the counter electrodes (discharge space) 6, and a power source is connected between the counter electrodes. A high frequency voltage was applied from 4 to obtain an excited discharge gas G ′. The source gas (C ₂ H ₂ gas) is supplied from the source gas supply means 7 to the source gas supply path 8 and sent to the mixing region 9 in a state parallel to the base material (PEN) F, and the excited discharge gas G ′ and The secondary excitation gas 10 was formed by mixing outside the discharge space, and the substrate F was exposed to the secondary excitation gas 10 to form the carbon film 11.

[Preparation of Sample 2]
Sample 2 was prepared in the same manner as in the preparation of Sample 1 except that 10 sccm of hydrogen gas was further added as a reaction gas to the discharge gas.

[Preparation of Sample 3]
Sample 3 was prepared in the same manner as in the preparation of Sample 1, except that CH ₄ was used instead of C ₂ H ₂ as the source gas.

[Preparation of Sample 4]
Two-frequency plasma jet type atmospheric pressure plasma treatment in which the raw material gas shown in FIG. 3 is supplied horizontally to an electrode on a polyethylene naphthalate film (Teijin-DuPont film) having a thickness of 100 μm as a substrate. Using the apparatus, a carbon film having a thickness of 200 nm was formed under the following gas conditions and discharge conditions, and Sample 4 was obtained.

<Power supply conditions>
First power supply: high frequency side 27.12 MHz 6 W / cm ²
Second power supply: low frequency side 100 kHz 5 w / cm ²
<Electrode conditions>
The square electrodes of the first electrode 3a and the second electrode 3b were manufactured by subjecting a 30 mm square hollow titanium pipe to ceramic spraying as a dielectric.

Dielectric thickness: 1mm
Electrode width: 300mm
Applied electrode temperature: 90 ° C
<Gas conditions>
Discharge gas: N ₂ , 100 slm
Source gas: C ₂ H ₂ , 200 sccm
Using the plasma jet type atmospheric pressure plasma processing apparatus 2 shown in FIG. 3, the discharge gas G (N ₂ gas) is supplied from the discharge gas supply means 5 between the counter electrodes (discharge space) 6 and between the counter electrodes. A high frequency voltage was applied to obtain an excitation discharge gas G ′. The source gas (C ₂ H ₂ gas) is supplied from the source gas supply means 7 to the source gas supply path 8 and sent to the mixing region 9 in a state parallel to the base material (PEN) F, and the excited discharge gas G ′ and The secondary excitation gas 10 was formed by mixing outside the discharge space, and the substrate F was exposed to the secondary excitation gas 10 to form the carbon film 11.

[Preparation of Sample 5]
Sample 5 was prepared in the same manner as in the preparation of Sample 4, except that 10 sccm of oxygen gas was further added as a reaction gas to the discharge gas.

[Preparation of Sample 6]
A gas mixture prepared by mixing discharge gas (Ar) and source gas (C ₂ H ₂ ) using the single-frequency plasma jet atmospheric pressure plasma processing apparatus shown in FIG. MG is supplied between the counter electrodes (discharge space) 6 from the mixed gas supply means (using the discharge gas supply means 5), and a high frequency voltage is applied between the counter electrodes from the power source 4 to form an excited mixed gas. Sample 6 was produced in the same manner except that the carbon film was formed by exposing the substrate to the excited mixed gas G ′.

[Preparation of Sample 7]
Sample 7 was prepared in the same manner as in the preparation of Sample 6, except that 10 sccm of hydrogen gas was further added as a reaction gas to the mixed gas.

[Preparation of Sample 8]
Sample 8 was prepared in the same manner as in the preparation of Sample 6 except that CH ₄ was used instead of C ₂ H ₂ as the source gas.

[Preparation of Sample 9]
In the production of the sample 4, instead of the plasma jet type atmospheric pressure plasma processing apparatus shown in FIG. 3, the plasma jet type atmospheric pressure plasma processing apparatus shown in FIG. _The mixed gas MG prepared by mixing ₂ H ₂ ) is supplied from the mixed gas supply means to the counter electrode (discharge space) 213, and a high frequency voltage is applied between the counter electrodes from the two-frequency power sources 227 and 228. Sample 9 was prepared in the same manner except that a carbon film was formed by exposing the substrate to this excited mixed gas MG ′ and forming a carbon film. At this time, a high frequency power source of 13.56 MHz 6 W / cm ² was used as the first power source on the high frequency side.

[Production of Sample 10]
Sample 10 was prepared in the same manner as in the preparation of Sample 9, except that 10 sccm of oxygen gas was further added as a reaction gas to the mixed gas.

<< Evaluation of each sample >>
The following evaluations were performed on each sample having the carbon film prepared above.

[Evaluation of sliding property: measurement of friction coefficient]
The dynamic friction coefficient of the carbon film surface of each sample was measured according to the method described in JIS-K-7125-ISO8295. A specimen made of stainless steel having a weight of 200 g is placed on the surface of the carbon film of each specimen, and the specimen is pulled horizontally under the conditions of a specimen moving speed of 100 mm / min and a contact area of 80 mm × 200 mm. ) And the dynamic friction coefficient (μ) was determined from the following formula.

Coefficient of dynamic friction = F (N) / weight of weight (N)
If the dynamic friction coefficient measured by the above method was less than 0.4, it was judged as ○, and if it was 0.4 or more, it was judged as ×.

[Evaluation of surface smoothness: measurement of surface roughness Ra]
The surface roughness Ra (nm) of the carbon film surface of each sample was measured according to the following method.

  As an atomic force microscope (AFM), the SPI3800N probe station and SPA400 multifunctional unit manufactured by Seiko Instruments Inc./SII Nanotechnology Co., Ltd. were used as measuring devices. DF20 was used. In the DFM mode (Dynamic Force Mode), a 10 μm square measurement area was measured, and the average roughness Ra (nm) was calculated from the obtained three-dimensional data.

[Evaluation of adhesion]
A cross-cut test based on JIS K5400 was performed. On the surface of the carbon film film of each sample, a single-edged razor blade was cut at 90 degrees with respect to the surface, 11 pieces vertically and horizontally at intervals of 1 mm, and 100 1-mm square grids were produced. A commercially available cellophane tape is affixed to this, and one end of the tape is peeled off vertically by hand, and the ratio of the peeled area of the carbon film to the affixed tape area from the score line is measured. Was evaluated.

○: Area ratio of peeled grid is 1% or less Δ: Area ratio of peeled grid is 2% or more and less than 10% ×: Area ratio of peeled grid is 10% or more The results are shown in Table 1.

  As is clear from the results shown in Table 1, the sample of the present invention in which the carbon film was formed by the gas supply method according to the present invention was different from the comparative example in that the formed carbon film had a low friction coefficient and surface smoothness. It can be seen that the adhesion to the substrate is good.

Example 2
In the production of Samples 1, 2, 4, 5, 6, 7, 9, and 10 described in Example 1 above, a carbon film was prepared in the same manner except that ethyl alcohol was used instead of C ₂ H ₂ as a source gas. As a result of evaluating the smoothness, surface smoothness and adhesion in the same manner as in Example 1, the same results as those shown in Table 1 were obtained.

Example 3
In the preparation of Samples 1 to 10 described in Example 1 above, a carbon film was formed in the same manner except that the substrate was replaced with PEN and a substrate having a silicon oxide film on PEN was used. As a result of evaluating the smoothness, surface smoothness, and adhesion by the same method as in No. 1, results similar to those shown in Table 1 could be obtained.

Example 4
In the preparation of Samples 1 to 5 described in Example 1, the carbon film was formed in the same manner except that the carbon film was formed by containing 5% by volume of nitrogen gas and argon gas as carrier gases in the source gas. As a result of evaluating the smoothness, the surface smoothness and the adhesiveness in the same manner as in Example 1, better results than those shown in Table 1 could be obtained.

Example 5
<Preparation of intermediate transfer member>
[Preparation of substrate]
A substrate for an intermediate transfer member was produced according to the following method.

Polyphenylene sulfide resin (E2180, manufactured by Toray Industries, Inc.) 100 parts by mass Conductive filler (Furness # 3030B, manufactured by Mitsubishi Chemical Corporation) 16 parts by mass Graft copolymer (Modiper A4400, manufactured by NOF Corporation) 1 part by mass Lubricant (calcium montanate) 0.2 parts by mass Each of the above raw materials was put into a single screw extruder and melt-kneaded to obtain a resin mixture. Next, a slit-shaped annular die having a seamless belt-shaped discharge port was attached to the tip of the single screw extruder, and the kneaded resin mixture was extruded into a seamless belt shape. The extruded seamless belt-shaped resin mixture is extrapolated to a cylindrical cooling cylinder provided at the discharge destination, cooled and solidified to form a base material for a seamless cylindrical intermediate transfer member with a thickness of 120 μm. Produced.

[Preparation of Intermediate Transfer Member 1]
Using the atmospheric pressure plasma processing apparatus 102a comprised of the atmospheric discharge part 103 and the substrate conveying unit shown in FIGS. While being supplied, a carbon film having a thickness of 200 nm was formed under the following formation conditions in the same manner as in the preparation of Sample 4 described in Example 1.

<Power supply conditions>
1st power supply 121a: High frequency side 27.12MHz 6W / cm < ² >
Second power supply 121b: low frequency side 100 kHz 5 w / cm ²
<Electrode conditions>
The square electrodes of the first electrode 121a and the second electrode 121b were manufactured by performing ceramic spraying as a dielectric on a 30 mm square hollow titanium pipe.

Dielectric thickness: 1mm
Electrode width: 300mm
Applied electrode temperature: 90 ° C
<Gas conditions>
Discharge gas: N ₂ , 100 slm (supplied from the discharge gas supply means 124 via the gas supply path 123)
Source gas: C ₂ H ₂ , 200 sccm (supplied from source gas supply means 127 via gas supply path 113)
[Preparation of Intermediate Transfer Member 2]
In the production of the intermediate transfer member 1, a discharge gas and a raw material gas are mixed to form a mixed gas, and this mixed gas is supplied from the gas supply means 124 via the gas supply path 123 to be an excited mixed gas. The intermediate transfer member 2 was produced in the same manner except that a carbon film was formed by exposing the cylindrical substrate 175 to the substrate.

<Evaluation of intermediate transfer member>
[Evaluation of smoothness, surface smoothness and adhesion]
According to the evaluation of the smoothness, surface smoothness, and adhesion of each intermediate transfer member in accordance with the method described in Example 1, the intermediate transfer member 1 was compared with the intermediate transfer member 2 and in any characteristics. It was confirmed that it had excellent results.

[Image quality evaluation by electronic copier]
As an electronic copying machine, a magiccolor 5440DL manufactured by Konica Minolta Business Technology was used, the internal intermediate transfer belt was removed, and the intermediate transfer belts 1 and 2 produced above were mounted. As a monochrome toner, a polymerization toner having an average particle diameter of 6.5 μm was used, and the density of a black solid image was changed in five levels from low to high on Konica Minolta Copy Paper NR-A80 (manufactured by Konica Minolta Business Technology). As a result of printing using a manuscript and visually observing unevenness and toner density of the output image, it is confirmed that the intermediate transfer body 1 has superior image quality formability compared to the intermediate transfer body 2. I was able to.

[Evaluation of cleaning suitability]
After cleaning the surface of each intermediate transfer member with a cleaning blade using the electronic copying machine, the surface state of each intermediate transfer member was visually observed to confirm the adhesion state of the toner, and the cleaning suitability was evaluated. It was confirmed that the intermediate transfer member 1 had excellent cleaning characteristics as compared with the intermediate transfer member 2.

It is the schematic which shows an example of the conventional atmospheric pressure plasma processing apparatus which introduces mixed gas of source gas and discharge gas in discharge space, and forms excitation gas in discharge space. It is the schematic which shows an example of the atmospheric pressure plasma processing apparatus which can be applied to this invention. It is the schematic which shows another example of the atmospheric pressure plasma processing apparatus which can be applied to this invention. It is the schematic which shows an example which applied the carbon film formation method of this invention to preparation of the intermediate transfer body for electrophotography. FIG. 5 is a schematic diagram in which a broken line portion (atmospheric pressure plasma processing apparatus 103) of the intermediate transfer body manufacturing apparatus shown in FIG. 4 is extracted. It is a perspective view which shows an example of a fixed electrode.

Explanation of symbols

2,210 Atmospheric pressure plasma processing apparatus 3a, 211 First electrode 3b, 212 Second electrode 4, 21, 22 Power source 5 Discharge gas supply means 6, 123 Discharge space 7 Source gas supply means 8, 113 Source gas supply path 9 Mixing Region 10 Secondary excitation gas 11 Carbon film 12 Waste gas 13 Exhaust gas path 21, 221 First power source 22, 222 Second power source 102 Intermediate transfer body manufacturing device 103 Atmospheric pressure plasma CVD device 120 Roll 121, 221 Fixed electrode 201 Driven roller 223 First filter 224 Fourth filter 225, 226 High-frequency voltage probe 227, 228 Oscilloscope F, 175 Base material G Discharge gas G ′ Excited discharge gas M Source gas

Claims (9)

A step of introducing a discharge gas into a discharge space and exciting it under atmospheric pressure or a pressure near atmospheric pressure, the excited discharge gas, and a raw material gas containing carbon introduced horizontally to the substrate, A step of mixing in the vicinity of the base material outside the discharge space to form a secondary excitation gas; and a step of forming a carbon film on the base material by exposing the base material to the secondary excitation gas. A carbon film forming method. The carbon film forming method according to claim 1, wherein the source gas containing carbon is a gas containing hydrocarbon or alcohol. The carbon film forming method according to claim 1, wherein the discharge space is formed by applying a high-frequency voltage between opposing electrodes. The carbon film forming method according to claim 3, wherein the high-frequency voltage has a frequency of 10 kHz or more and 10 GHz or less. The discharge gas is 1) nitrogen gas, 2) noble gas, 3) oxygen gas, carbon dioxide gas, chlorine gas, hydrogen gas, and nitrogen gas containing at least one gas selected from metal-containing gas, or 4) oxygen The carbon film formation according to any one of claims 1 to 4, wherein the carbon film is a rare gas containing at least one gas selected from gas, carbon dioxide gas, chlorine gas, hydrogen gas, and metal-containing gas. Method. The carbon film forming method according to claim 1, wherein the base material is a polymer film or a polymer film having a metal-containing thin film as an outermost layer. The carbon film forming method according to claim 1, wherein the source gas containing carbon contains nitrogen gas or a rare gas as a carrier gas. The carbon film forming method according to claim 3, wherein the high-frequency voltage has a frequency of 1 GHz or more and 10 GHz or less. The carbon film forming method according to claim 1, wherein the carbon film has a hydrogen atom content of 30 atomic% or more.

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