JP2005163062A - Plasma cvd film deposition apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To realize the consistent operation of a plasma CVD film deposition apparatus for a long time by reducing the residual energy of exhaust gas exhausted from a vacuum chamber to suppress degradation of an exhaust path. <P>SOLUTION: A plasma CVD film deposition apparatus comprises a vacuum chamber to store a plastic container, a raw gas feed means to feed raw gas to at least one of an internal space of the plastic container and an external space of the plastic container, a plasma generating means to supply high frequency waves or microwaves to plasmatize the raw gas, and an exhaust means which is connected to the vacuum chamber and provided with at least an exhaust mans to exhaust the raw gas, and deposits a CVD film on at least one of an inner surface and an outer surface of the plastic container. A conductive member with permeability is arranged in an exhaust path to make the vacuum chamber communicate with the exhaust means. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a plasma CVD film forming method for coating a CVD film, for example, a DLC (diamond-like carbon) film, on at least one of an inner surface and an outer surface of a plastic container by a CVD (Chemical Vapor Deposition) method. Relates to the device.

  In order to deposit a DLC film on the inner surface of a plastic container for the purpose of improving gas barrier properties, etc., there is a disclosure of an invention of a vapor deposition apparatus using a CVD method, particularly a plasma CVD method (see, for example, Patent Document 1). In the apparatus described in Patent Document 1, a plastic container is disposed in a vacuum chamber, and a high frequency is applied to an external electrode that constitutes a part of the vacuum chamber in a state in which a raw material gas is flowed inside the container. As a result, a bias voltage is generated between the internal electrode and the external electrode arranged inside the container, and the source gas is turned into plasma, and a CVD film is formed on the inner surface of the container. The raw material that has been turned into plasma is exhausted out of the vacuum chamber by the exhaust means of the vacuum chamber.

JP-A-8-53117

  In a plasma CVD film forming apparatus that forms a CVD film on the wall surface of a plastic container, using the CVD film forming apparatus of Patent Document 1 as an example, the material gas is converted into plasma inside the plastic container and film formation is performed. Here, in such a film forming apparatus, the raw material gas remaining without being consumed as a CVD film or a source gas containing a carrier gas such as argon is exhausted from a vacuum chamber which is a film forming chamber. However, the present inventors have found that these exhaust gases still have residual energy due to the plasma, and attack the exhaust path from the film formation chamber to the vacuum pump, so that metal parts such as pipes and pipe joints can be used. It has been found that non-metallic parts used in the industry are deteriorated. Therefore, an object of the present invention is to shield the plasma diffusing to the exhaust path side with an air-permeable conductive member, thereby reducing the residual energy of the exhaust gas exhausted from the vacuum chamber and then allowing it to permeate and exhaust. Therefore, it is intended to suppress the deterioration of the exhaust path and realize long-term stable operation of the plasma CVD film forming apparatus.

  The inventors of the present invention can reduce the residual energy of the exhaust gas and prevent the attack to the exhaust path by disposing a conductive member having air permeability in the exhaust path and allowing the exhaust gas to pass through the conductive member. The present invention was completed.

  That is, a plasma CVD film forming apparatus according to the present invention includes a vacuum chamber that accommodates a plastic container, and source gas supply means that supplies source gas to at least one of the internal space of the plastic container or the external space of the plastic container. A plasma generating means for supplying a high frequency or a microwave for converting the raw material gas into a plasma, and an exhaust means connected to the vacuum chamber for exhausting the raw material gas, the inner surface or the outer surface of the plastic container. In a plasma CVD film forming apparatus for forming a CVD film on at least one of the surfaces, a conductive member having air permeability is disposed in an exhaust path communicating the vacuum chamber and the exhaust unit.

  In the plasma CVD film forming apparatus according to the present invention, the conductive member is preferably a laminate of a plurality of metal meshes, punching metals, or expanded metals. Here, it is more preferable that the conductive member has 2 to 10 metal meshes, punching metal, or expanded metal, and is arranged with an interval. Or it is more preferable that the said electrically-conductive member is what consists of what wound the metal ribbon irregularly, or consists of metal irregular fillers.

  In the plasma CVD film-forming apparatus according to the present invention, the conductive member is preferably a columnar metal provided with a plurality of thin tubes having openings at the upper and lower bases. The present invention provides another form of the conductive member for reducing the residual energy of the exhaust gas from which the plasma has substantially disappeared.

  Furthermore, in the plasma CVD film forming apparatus according to the present invention, the hole diameter of the conductive member is more preferably 1 to 10 mm. Such a hole diameter is used to effectively reduce the residual energy of the exhaust gas and prevent an increase in exhaust resistance due to pressure loss.

  The present invention reduces the residual energy of the plasma that diffuses toward the exhaust path, thereby suppressing deterioration of the exhaust path and realizing a long-term stable operation of the plasma CVD film forming apparatus.

  Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not construed as being limited to these embodiments. Moreover, the same code | symbol was attached | subjected when the member was common in each drawing. Embodiments of the present invention will be described below with reference to FIGS.

  FIG. 1 is a conceptual diagram showing an embodiment of a plasma CVD film forming apparatus according to the present invention. The plasma CVD film forming apparatus according to the present invention supplies a vacuum chamber 6 containing a plastic container 7, a raw material gas supply means 18 for introducing a raw material gas to be converted into plasma into the plastic container 7, and a high frequency to the external electrode 3. The plasma generating means 12 for converting the raw material gas into plasma and the exhaust means 28 connected to the vacuum chamber 6 and exhausting the raw material gas are provided, and a CVD film is formed on the inner surface of the plastic container 7. .

  As shown in FIG. 1, the vacuum chamber 6 includes an external electrode 3 that accommodates a plastic container 7, an internal electrode 9 that is removably disposed inside the plastic container 7, and a lid 5, and is a sealable vacuum chamber. Form. The vacuum chamber becomes a film forming chamber.

  The lid 5 includes a conductive member 4b and an insulating member 4a. When the internal electrode 9 is inserted into the plastic container 7, the internal electrode 9 and the external electrode 3 are insulated. An insulating member 4a is disposed under the conductive member 4b to form a lid 5, and the external electrode 3 is disposed under the insulating member 4a. The lid 5 is provided with an opening that leads to a space for accommodating the external electrode 3. Further, a space is provided inside the lid 5, and this space is connected to a housing space for the external electrode 3 through the opening.

  The external electrode 3 includes an upper external electrode 2 and a lower external electrode 1 and accommodates a plastic container 7. The upper part of the lower external electrode 1 is detachably attached to the lower part of the upper external electrode 2 via an O-ring 8. The plastic container 7 can be mounted by detaching the upper external electrode 2 and the lower external electrode 1. A space is formed inside the external electrode 3, and this accommodation space is an accommodation space for accommodating a plastic container 7 to be coated, for example, a PET bottle which is a container made of polyethylene terephthalate resin. The accommodation space of the external electrode 3 is sealed from the outside by an O-ring 8 disposed between the upper external electrode 2 and the lower external electrode 1.

  The internal electrode 9 is detachably disposed in the external electrode 3 and disposed in the plastic container 7. That is, the internal electrode 9 is inserted into the housing space of the external electrode 3 from the upper part of the conductive member 4b through the space in the conductive member 4b and the openings of the conductive member 4b and the insulating member 4a. The base end of the internal electrode 9 is disposed on the upper part of the conductive member 4b. On the other hand, the tip of the internal electrode 9 is disposed inside the plastic container 7. The internal electrode 9 has a tube shape whose inside is hollow. The internal electrode 9 also serves as a source gas supply nozzle. That is, a gas blowing port 49 is provided at the tip of the internal electrode 9. Further, the internal electrode 9 is grounded. A gas outlet may be provided on the side cylinder of the internal electrode 9.

  The container according to the present invention includes a container that is used with a lid, a stopper, or a seal, or a container that is used without being used. The size of the opening is determined according to the contents. The plastic container includes a plastic container having a predetermined thickness having moderate rigidity and a plastic container formed by a sheet material having no rigidity. Examples of the filling material of the plastic container according to the present invention include beverages such as carbonated beverages, fruit juice beverages, and soft drinks, and pharmaceuticals, agricultural chemicals, and dry foods that dislike moisture absorption.

  Resin used when molding the plastic container of the present invention is polyethylene terephthalate resin (PET), polyethylene terephthalate-based copolyester resin (copolymer using cyclohexane dimethanol instead of ethylene glycol as the alcohol component of polyester) Called Eastman Chemical), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin (PP), cycloolefin copolymer resin (COC, cyclic olefin copolymer), ionomer resin, poly-4-methyl Pentene-1 resin, polymethyl methacrylate resin, polystyrene resin, ethylene-vinyl alcohol copolymer resin, acrylonitrile resin, polyvinyl chloride resin, polyvinyl chloride Resins, polyamide resins, polyamide-imide resins, polyacetal resins, polycarbonate resins, polysulfone resins, or ethylene tetrafluoride resin, acrylonitrile - styrene resins, acrylonitrile - butadiene - styrene resin, can be exemplified. Among these, PET is particularly preferable.

  The raw material gas supply means 18 introduces the raw material gas supplied from the raw material gas generation source 17 into the plastic container 7. That is, one side of the pipe 13 is connected to the base end of the internal electrode 9, and the other side of the pipe 13 is connected to one side of the mass flow controller 15 via the vacuum valve 14. The other side of the mass flow controller 15 is connected to a source gas generation source 17 via a pipe 16. The source gas generation source 17 generates hydrocarbon gas such as acetylene.

  As the source gas, for example, when a DLC film is formed, aliphatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons, etc. that are gaseous or liquid at room temperature are used. In particular, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexane and the like having 6 or more carbon atoms are desirable. When used for food containers, aliphatic hydrocarbons from the viewpoint of hygiene, especially ethylene hydrocarbons such as ethylene, propylene or butylene, or acetylene hydrocarbons such as acetylene, arylene or 1-butyne Is preferred. These raw materials may be used alone, or may be used as a mixed gas of two or more. Further, these gases may be diluted with a rare gas such as argon or helium. In addition, when a silicon-containing DLC film is formed, a Si-containing hydrocarbon gas is used.

The DLC film referred to in the present invention is a film called i-carbon film or hydrogenated amorphous carbon film (aC: H), and includes a hard carbon film. The DLC film is an amorphous carbon film and also has SP ³ bonds. A hydrocarbon gas such as acetylene gas is used as a source gas for forming the DLC film, and a Si-containing hydrocarbon gas is used as a source gas for forming the Si-containing DLC film. By forming such a DLC film on the inner surface of a plastic container, a container that can be used in a one-way and returnable manner as a container for carbonated beverages, sparkling beverages, and the like is obtained.

  The exhaust means 28 is connected to the vacuum chamber 6 and exhausts the source gas. A space in the conductive member 4 b which is a part of the vacuum chamber 6 is connected to one side of a pipe 23 constituting an exhaust path, and the other side of the pipe 23 is connected to a vacuum pump 26 via a vacuum valve 25. ing. This vacuum pump 26 is further connected to an exhaust duct 27. A gas-permeable conductive member 22 and a pressure gauge 24 are disposed in a pipe 23 that is an exhaust path that communicates the vacuum chamber 6 with an exhaust unit 28 that includes a vacuum pump 26 and an exhaust duct 27. The pressure gauge 24 detects the pressure in the exhaust path.

  The piping 23 serving as an exhaust path is formed by piping components such as a joint from the vacuum chamber 6 to the exhaust means 28. Here, the exhaust gas from the vacuum chamber 6 including the raw material gas remaining without being consumed as the CVD film or the raw material gas containing a carrier gas such as argon still has residual energy due to plasma formation. If this residual energy remains, the exhaust path from these film forming chambers to the vacuum pump is attacked, and metal parts such as pipes and non-metal parts used in pipe joints are deteriorated. When the deterioration occurs, problems such as gas leakage occur, and the long-term stable operation of the plasma CVD film forming apparatus becomes impossible. Therefore, the conductive member 22 is provided to remove the residual energy of the exhaust gas. The conductive member 22 is preferably grounded via the pipe 23.

  As shown in FIGS. 2 to 4, examples of the conductive member 22 include a wire mesh, punching metal, or expanded metal disposed in a pipe 23 that is an exhaust path. FIG. 2 is a schematic view showing a form example when an air-permeable conductive member is arranged in the exhaust path, and shows a case where three metal meshes are stacked. FIG. 3 is a schematic view showing a form example when an air-permeable conductive member is arranged in the exhaust path, and shows a case where two punching metals are stacked. FIG. 4 is a schematic view showing a form example when a breathable conductive member is arranged in the exhaust path, and shows a case where two expanded metals are stacked. When the conductive member 22 is a wire mesh, punching metal, or expanded metal, the number of stacked members is preferably 2 to 10. If the number is one, the residual energy of the exhaust gas cannot be removed sufficiently. At this time, there is a method of reducing the mesh of the wire mesh in order to reduce the residual energy, but the exhaust resistance due to pressure loss increases. On the other hand, if the number exceeds 10, the exhaust resistance increases and the capacity of the exhaust means 22 needs to be significantly increased. Further, it is preferable that the punching metal or the expanded metal be spaced apart from each other without being in contact with each other, and this spacing is preferably at least larger than the hole diameter of the conductive member 22. By providing a space between the conductive members 22, the exhaust gas is agitated in the piping of the exhaust path to increase the chance of contact. When the conductive member 22 is a wire mesh, punching metal, or expanded metal, its characteristics are determined by a hole shape such as a round shape, a square shape, a rectangular shape, a hole diameter, an aperture ratio, a material thickness, or a metal wire thickness. In the conductive member 22 of the present embodiment, wire nets, punching metal, or expanded metal having the same characteristics may be arranged side by side, or metal nets, punching metal, or expanded metal having different characteristics may be arranged side by side. The combination can be changed as appropriate. For example, as shown in FIG. 2, a wire mesh 22a with a sparse eye size d1 with respect to the flow of exhaust gas, a wire mesh 22b with a denser mesh size d2 and a wire mesh with a sparse eye size d1. Wire meshes 22 having different eye sizes may be alternately arranged in parallel with 22c. Further, as shown in FIG. 3, a punching metal 22d punched into a round shape having a hole diameter φ and a punching metal 22e punched into a rectangle having sides d1 and d2 may be arranged side by side. Further, as shown in FIG. 4, the conductive member 22 is formed by arranging an expanded metal 22f provided with holes having a center distance d1 in the long direction and a center distance d2 in the short direction and an expanded metal 22g identical to the expanded metal 22g. May be. Alternatively, the conductive member 22 may be fixed to the holding frame so that the conductive members are held at predetermined intervals, and the holding frame may be locked to the pipe 23. The hole diameter d of the conductive member is 1 to 10 mm, preferably 1.5 to 5 mm. If the hole diameter is less than 1 mm, the exhaust resistance is increased. On the other hand, if the hole diameter exceeds 10 mm, the chance of contact with the exhaust gas decreases, and the residual energy of the exhaust gas cannot be removed sufficiently. In addition, when the shape of the hole is a square, the center distance in the short direction is 1 to 5 mm, the center distance in the long direction is 3 to 10 mm, preferably the center distance in the short direction is 1.5 to 3 mm, and long. The center distance between the eyes is 3 to 5 mm. The expanded metal includes both the standard type and the grating type.

  Further, as illustrated in FIG. 5, the conductive member 22 can be exemplified by an irregularly wound metal ribbon shaped metal ribbon disposed in a pipe 23 that is an exhaust path. FIG. 5 is a schematic view showing another embodiment when a conductive member having air permeability is arranged in the exhaust path, and shows a case where an irregularly wound metal ribbon is arranged. When the conductive member 22 is an irregular winding of a metal scrubbing metal ribbon, the characteristics are determined by the thickness and width of the metal ribbon and the winding method of the metal ribbon. A plurality of conductive members 22, which are irregularly wound metal ribbons, may be arranged because of the thickness in the exhaust gas flow direction, but only one is arranged so as not to increase the exhaust resistance. Is preferred. In this case, the average hole diameter of the conductive member is 1 to 10 mm, preferably 1.5 to 5 mm.

  Furthermore, as illustrated in FIG. 6, the conductive member 22 can be exemplified by an assembly of a plurality of metal irregular fillers arranged in a pipe 23 serving as an exhaust path, and Rashihi Super Ring (Rahishi Corporation, registered trademark). Typical examples of metal irregular packings are packings used in absorption towers (physical absorption, chemical absorption), stripping towers and distillation towers. Can pass through. FIG. 6 is a schematic view showing another embodiment when a conductive member having air permeability is arranged in the exhaust path, and shows a case where an assembly of metal irregular fillers is arranged. When the conductive member 22 is an irregularly deformed hollow tube-like metal irregular filler, its characteristics are the tube diameter, length and thickness of the metal irregular filler, and the metal irregular filler. Determined by the shape. In this case, the average hole diameter of the conductive member, that is, the tube diameter is 1 to 10 mm, preferably 1.5 to 5 mm.

  Further, as shown in FIG. 7, the conductive member 22 can be exemplified by a pipe 23 serving as an exhaust path provided with a plurality of thin tubes 29 made of columnar metal and having openings at the upper and lower bases. FIG. 7 is a schematic view showing another embodiment when a conductive member having air permeability is arranged in the exhaust path, and a columnar metal made by providing a plurality of thin tubes having openings at the upper and lower bases. The case where it arranges is shown. When the conductive member 22 is a columnar metal and is provided with a plurality of thin tubes 29 having openings in the upper and lower bases, the characteristic is the height of the middle metal (distance between the upper and lower bases). , Determined by the hole diameter of the opening of the thin tube 29. In this case, the hole diameter of the opening is 1 to 10 mm, preferably 1.5 to 5 mm.

  Examples of the material of the conductive member described above include stainless steel, aluminum, titanium, gold, silver, and copper. In the same conductive member, the hole diameter may be the same, but in order to increase the opening area ratio, holes having different hole diameters may be provided in combination. The opening area ratio of the conductive member is preferably 40% to 70% in order to suppress an increase in ventilation resistance.

  The plasma generating means 12 supplies high frequency to the external electrode 3 to turn the source gas into plasma. The plasma generating means 12 includes a high frequency power source 11 and an automatic matching unit 10 connected to the high frequency power source 11, and the high frequency power source 11 is connected to the external electrode 3 via the automatic matching unit 10. The high-frequency power source 11 generates a high-frequency voltage between the internal electrode 9 and the external electrode 3 by generating a high-frequency voltage with respect to the ground potential. As a result, the raw material gas supplied into the plastic container 7 is turned into plasma. The frequency of the high-frequency power source is 100 kHz to 1000 MHz, and for example, an industrial frequency of 13.56 MHz is used.

  The vacuum chamber 6 is connected to a leak pipe 19, and the pipe 19 communicates with a leak source 21 (open to the atmosphere) via a vacuum valve 20.

  The present embodiment is not limited to the plasma CVD film forming apparatus of the type that supplies a high frequency to the external electrode shown in FIG. For example, without providing an internal electrode, a raw material gas supply nozzle is arranged inside a plastic container, and the raw material gas supplied into the plastic container is directly irradiated with microwaves (for example, frequency 2450 MHz) to turn the raw material gas into plasma. There is a CVD film forming apparatus. This apparatus is a type of plasma CVD film forming apparatus that forms a CVD film on the inner surface of a plastic container. However, the conductive member 22 may be disposed in the exhaust path of the apparatus. Also, a CVD film forming apparatus that does not provide an internal electrode, and a source gas supply nozzle is disposed outside the plastic container, and the source gas supplied to the outside of the plastic container is directly irradiated with microwaves to turn the source gas into plasma. There is also. This apparatus is a type of plasma CVD film forming apparatus for forming a CVD film on the outer surface of a plastic container. However, the conductive member 22 may be arranged in the piping of the exhaust path of this apparatus. The present invention is not limited by whether a CVD film is formed on the inner surface, outer surface, or both surfaces of the container, or whether the method of converting the raw material into plasma uses high frequency or microwaves.

  Next, a method for forming a DLC film inside the container using the plasma CVD film forming apparatus shown in FIG. 1 will be described. The inside of the vacuum chamber 6 is opened to the atmosphere by opening the vacuum valve 20, and the lower external electrode 1 of the external electrode 3 is removed from the upper external electrode 2. The plastic container 7 is inserted into the space in the upper external electrode 2 from the lower side of the upper external electrode 2 and installed. At this time, the internal electrode 9 is inserted into the plastic container 7. Next, the lower external electrode 1 is attached to the lower part of the upper external electrode 2, and the external electrode 3 is sealed with an O-ring 8.

  Next, the inside of the plastic container 7 is replaced with a raw material gas and adjusted to a predetermined film forming pressure. That is, as shown in FIG. 1, after the vacuum valve 20 is closed, the vacuum valve 25 is opened and the vacuum pump 26 is operated. Thereby, the inside of the vacuum chamber 6 including the inside of the plastic container 7 is exhausted through the pipe 23, and the inside of the vacuum chamber 6 is evacuated. The pressure in the vacuum chamber 6 at this time is 2.6 to 66 Pa.

  Next, the vacuum valve 14 is opened, a hydrocarbon gas such as acetylene gas is generated in the source gas generation source 17, the hydrocarbon gas is introduced into the pipe 16, and the hydrocarbon gas whose flow rate is controlled by the mass flow controller 15 is introduced. The gas is blown out from the gas outlet 49 through the pipe 13 and the internal electrode 9 at the ground potential. As a result, hydrocarbon gas is introduced into the plastic container 7. The inside of the vacuum chamber 6 and the plastic container 7 are maintained at a pressure suitable for DLC film formation (for example, about 6.6 to 665 Pa) and stabilized by the balance between the controlled gas flow rate and the exhaust capability.

  Next, a high frequency output is supplied to the external electrode 3 to make the source gas into plasma in the plastic container 7 to form a DLC film on the inner surface of the plastic container 7. That is, the vacuum chamber 6 is supplied with RF output (for example, 13.56 MHz) by the plasma generating means 12. As a result, a bias voltage is generated between the external electrode 3 and the internal electrode 9 and the raw material gas in the plastic container 7 is turned into plasma to generate hydrocarbon-based plasma, and a DLC film is formed on the inner surface of the plastic container 7. Is done. At this time, the automatic matching unit 10 matches the impedance by the inductance L and the capacitance C so that the reflected wave from the entire electrode supplying the output is minimized. The film formation time at this time is as short as several seconds. The DLC film is formed to have a thickness of 0.003 to 5 μm.

  Next, the RF output from the plasma generating means 12 is stopped, the plasma is extinguished, and the DLC film formation is completed. Almost simultaneously, the vacuum valve 14 is closed to stop the supply of the raw material gas.

  Next, in order to remove the hydrocarbon gas remaining in the vacuum chamber 6 and the plastic container 7, the vacuum valve 25 is opened, and the hydrocarbon gas in the vacuum chamber 6 and the plastic container 7 is exhausted by the vacuum pump 26. Thereafter, the vacuum valve 25 is closed, and the exhaust is finished. The pressure in the vacuum chamber 6 at this time is 6.6 to 665 Pa. Thereafter, the vacuum valve 20 is opened. Thereby, the vacuum chamber 6 is opened to the atmosphere.

  During application of the high frequency in the film forming process, the source gas is converted into plasma between the external electrode 3 and the internal electrode 9, that is, inside the plastic container 7. Since the source gas continues to be supplied, the source gas after film formation is discharged from the container mouth, and exhausted through the space inside the lid 5 to the pipe 23 serving as an exhaust path. The source gas after film formation is away from the internal electrode 9 and the external electrode 3 when being exhausted from the vacuum chamber, so that the plasma is almost lost. However, when the conductive member 22 having air permeability is not provided in the piping 23 of the exhaust path, the components of the exhaust path are attacked by the residual energy of the exhaust gas. In addition, as a component, the packing which consists of fluoroelastomer, fluororubber (trademark Viton), etc. can be illustrated. When 100 film formations were performed in 2 seconds for one film formation, leakage was detected from the pipe 23. Here, in the case where one 3 mm mesh wire mesh is disposed as the conductive member 22, leakage is detected from the pipe 23 when the film formation is performed 100 times in 1 second for 2 seconds. Accordingly, it has been found that if one 0.5 mm mesh wire mesh is disposed, the exhaust resistance increases, and it is not suitable for placement in the piping of the exhaust path. Therefore, when the conductive member 22 is arranged with two 3 mm mesh metal meshes arranged in parallel, no leakage was detected from the pipe 23 even if the film was formed 5000 times in 1 second. By arranging two 3 mm mesh metal meshes in parallel, it was possible to effectively reduce the residual energy from the exhaust gas while suppressing an increase in exhaust resistance. The same effect was obtained even when the number of wire meshes was increased to 10. 2 to 7, no leakage was detected from the pipe 23 even when the film formation was performed 5000 times in 1 second for 2 seconds. As a result, the occurrence of gas leakage from the exhaust pipe is prevented, and the apparatus can be operated for a long time.

  When the opening area ratio of the conductive member 22 is 50%, there is almost no increase in exhaust resistance, and the oxygen permeability of the obtained DLC film-coated plastic container (700 ml) is 0.003 ml / day / container. The level was the same as when the film was formed without providing the conductive member 22. The evacuation time was 3.0 seconds, which was the same level as when the film was formed without providing the conductive member 22.

It is a conceptual diagram which shows one form of the CVD film-forming apparatus which concerns on this invention. It is the schematic which shows the example of a mode when the electrically conductive member which has air permeability is arrange | positioned in an exhaust path | route, Comprising: The case where three metal nets are piled up is shown. It is the schematic which shows the example of a form when the electrically conductive member which has air permeability is arrange | positioned in an exhaust path | route, Comprising: The case where two sheets of punching metals are accumulated is shown. It is the schematic which shows the example of a form when the electrically conductive member which has air permeability is arrange | positioned in an exhaust path | route, Comprising: The case where two sheets of expanded metal are piled up is shown. It is the schematic which shows another form when the electrically conductive member which has air permeability is arrange | positioned in an exhaust path | route, Comprising: The case where what wound the metal ribbon irregularly is shown. It is the schematic which shows another form when the electrically conductive member which has air permeability is arrange | positioned in an exhaust path, Comprising: The case where the aggregate | assembly of metal irregular fillers is arrange | positioned is shown. It is a schematic diagram showing another form when a conductive member having air permeability is arranged in the exhaust path, and a case where a columnar metal having a plurality of thin tubes having openings at the upper and lower bases is arranged. Show.

Explanation of symbols

1, lower external electrode 2, upper external electrode 3, external electrode 4a, insulating member 4b, conductive member 5, lid 6, vacuum chamber,
7. Plastic container (PET bottle)
8, O-ring 9, internal electrode 10, automatic matching unit 11, high frequency power supply (RF power supply)
12, plasma generation means 13, 16, 19, 23, piping 14, 20, 25, vacuum valve 15, mass flow controller 17, source gas generation source 18, source gas supply means 21, leak gas (air) supply source 22, air permeability Conductive member 24, pressure gauge 26, vacuum pump 27, exhaust duct 28, exhaust means 29, narrow tube

Claims (6)

A vacuum chamber containing a plastic container; raw material gas supply means for supplying a raw material gas to at least one of the internal space of the plastic container or the external space of the plastic container; and a high-frequency or microwave that converts the raw material gas into plasma At least one of an inner surface and an outer surface of the plastic container, and a plasma film is formed on at least one of the inner surface and the outer surface of the plastic container. In the plasma CVD film forming apparatus,
A plasma CVD film-forming apparatus, wherein a conductive member having air permeability is disposed in an exhaust path communicating the vacuum chamber and the exhaust means.   2. The plasma CVD film forming apparatus according to claim 1, wherein the conductive member is formed by stacking a plurality of metal meshes, punching metals, or expanded metals.   3. The plasma CVD film forming apparatus according to claim 1, wherein the conductive member has 2 to 10 metal meshes, punched metal, or expanded metal, and is disposed at an interval. 4.   2. The plasma CVD film forming apparatus according to claim 1, wherein the conductive member is made of an irregularly wound metal ribbon or a metal irregular filler.   2. The plasma CVD film forming apparatus according to claim 1, wherein the conductive member is a columnar metal provided with a plurality of thin tubes having openings in the upper and lower bases. 6. The plasma CVD film forming apparatus according to claim 1, wherein the hole diameter of the conductive member is 1 to 10 mm.

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