JP2005113202A - Plasma cvd film deposition system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To increase plasma density in a film deposition system where a CVD (Chemical Vapor Deposition) film is deposited at least either the inner surface or the outer surface of a plastic vessel. <P>SOLUTION: In the CVD film deposition system, the whole of the wall face in a space for storing a plastic vessel provided on an external electrode or a part of the wall face is provided with a secondary electron emission layer composed of a material having a secondary electron emission coefficient higher than that of an electrode material in the external electrode. Further, in an insulated state with the external electrode, the whole of the surface of an internal electrode arranged freely attachably/detachably at the inside of the vessel or a part of the surface is provided with a secondary electron emission layer composed of a material having a secondary electron emission coefficient higher than that of the electrode material in the internal electrode. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a plasma CVD film forming method for coating a CVD film, particularly 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 Patent Document 1, the external electrode has a void that is substantially similar to the outer shape of the container to be accommodated. The reason why the wall surface of the void of the external electrode and the outer surface of the plastic container are kept substantially in contact is to apply a self-bias voltage uniformly to the inner wall surface of the plastic container.

  If there is a place where the wall surface of the void of the external electrode is separated from the outer surface of the plastic container, the self-bias voltage is hardly applied to the separated part of the inner wall surface of the plastic container. Therefore, the source gas ions that have been converted to plasma during plasma ignition do not strongly collide with the inner wall surface of the container, a dense DLC film cannot be obtained, and the film quality becomes non-uniform. Further, when the wall surface of the void of the external electrode and the outer surface of the plastic container are separated from each other, no self-bias voltage is applied to the inner wall surface of the container, and even if a uniform film is formed, the film is a dense DLC. It is not a membrane. If a dense DLC film is not obtained, sufficient gas barrier properties cannot be obtained. For a container with many irregularities such as a heat-resistant container, the outer surface of the container and the wall surface of the cavity of the external electrode cannot be completely brought into contact with each other, and it is difficult to achieve sufficient gas barrier properties.

JP-A-8-53117

  If a high self-bias voltage can be applied to the inner wall surface of the container, it can be expected that the film becomes dense and, as a result, a film having good gas barrier properties. Here, as a means for increasing the self-bias voltage, a method of increasing the high-frequency power supplied to the external electrode can be considered. However, excessively high frequency power supply causes the plastic container to be thermally deformed and deteriorated. Therefore, if the plasma density can be increased without increasing the amount of high-frequency power supplied, the self-bias voltage can be increased without causing the above-described thermal deformation and thermal deterioration. As a result, the film can be densified, which is advantageous. In addition, the film formation rate can be increased by increasing the plasma density.

  The present invention relates to an apparatus for forming a CVD film on at least one of an inner surface and an outer surface of a plastic container, and an electrode of an external electrode or an internal electrode at a contact site between the generated plasma and the external electrode or the internal electrode. An object is to increase the plasma density by providing a secondary electron emission layer made of a material having a larger secondary electron emission coefficient than the material.

  In an apparatus for forming a CVD film on at least one of an inner surface and an outer surface of a plastic container, the present invention provides an external electrode on the entire wall surface or a part of the wall surface of the external electrode housing the plastic container. It has been found that by providing a secondary electron emission layer made of a material having a secondary electron emission coefficient larger than that of the electrode material, the plasma density of the plasma gas generated in the space outside the container in the void can be increased. Further, a secondary electron emission layer made of a material having a secondary electron emission coefficient larger than that of the electrode material of the internal electrode is formed on the entire surface or a part of the surface of the internal electrode serving as the ground electrode with respect to the external electrode supplying the high frequency power It has been found that the plasma density of the plasma gas generated inside the container can be increased in the same manner, and the present invention has been completed.

  That is, the plasma CVD film forming apparatus according to the present invention has a space for accommodating a plastic container, and the plastic container is placed in the space so that the gas inside the container and the gas outside the container do not cross each other. An external electrode that also serves as a vacuum chamber that can be housed in an internal electrode, an internal electrode that is insulated from the external electrode and is removably disposed inside the plastic container, and a source gas or a discharge gas for plasmatization A container internal gas introduction means for introducing the container internal gas into the plastic container, and a container external gas introduction means for introducing the container external gas, which is a raw material gas or a discharge gas for plasmatization, into the space, A high frequency supply means for supplying a high frequency to the external electrode, and a minimum of an inner surface or an outer surface of the plastic container. Is a plasma CVD film forming apparatus for forming a CVD film on either one of them, and has a secondary electron emission coefficient larger than the electrode material of the external electrode on the entire wall surface of the void of the external electrode or a part of the wall surface A secondary electron emission layer made of a material is provided.

  In the external electrode of the CVD film forming apparatus of Patent Document 1, the shape of the wall surface of the space has to be similar to the outer surface of the container. However, in the plasma CVD film forming apparatus according to the present invention, the shape of the wall surface of the space can be made free as long as the plastic container can be accommodated. That is, by supplying a gas outside the container into a space formed by the separation of the wall surface of the void of the external electrode and the outer surface of the container, and converting the gas outside the container into a plasma, The gas becomes a conductor and conducts high frequency to the outer surface of the container, thereby creating an approximate state in which the wall surface of the void is in contact with the outer surface of the plastic container. This makes it possible to apply a uniform self-bias voltage to the inner wall surface of the container. That is, a uniform and dense CVD film can be formed on the container wall surface by introducing the gas outside the container. Thereby, in a heat-resistant bottle having a reduced pressure absorption surface, a CVD film can be formed even if there is a gap between the wall surface of the void of the external electrode and the outer surface of the container. In addition, CVD films can be formed on plastic containers of various types without changing one type of external electrode. Furthermore, this plasma CVD film-forming apparatus can select only the inner surface of the container, only the outer surface of the container, or the inner and outer surfaces of the container by selecting the source gas or the discharge gas as the container inner gas and the container outer gas, respectively. A CVD film can be formed on both. Furthermore, when the container internal gas or the container external gas is used as the discharge gas, the wall surface of the plastic container can be subjected to plasma surface modification by the plasmaized discharge gas.

  Here, in the plasma CVD film forming apparatus according to the present invention, the secondary electron emission layer made of a material having a larger secondary electron emission coefficient than the electrode material of the external electrode is formed on the entire wall surface of the void of the external electrode or a part of the wall surface. Is provided. Thereby, many secondary electrons are emitted from the secondary electron emission layer toward the container external gas, and as a result, the plasma density of the container external gas can be increased. As a result, the self-bias voltage can be increased without causing thermal deformation or thermal deterioration of the plastic container. As a result, densification of the film can be realized.

  Here, in the plasma CVD film forming apparatus according to the present invention, a secondary electron emission layer made of a material having a secondary electron emission coefficient larger than the electrode material of the internal electrode is formed on the entire surface of the internal electrode or a part of the surface. It is preferable to provide it. As a result, many secondary electrons are emitted from the secondary electron emission layer toward the container inner gas and the container outer gas, and as a result, the plasma density of the container inner gas and the container outer gas that are turned into plasma can be increased. . By increasing the plasma density of the gas outside the container, the self-bias voltage on the container wall surface can be increased without causing thermal deformation / deterioration of the plastic container. As a result, densification of the film can be realized. Furthermore, by increasing the plasma density of the gas inside the container, it is possible to increase the deposition rate without causing thermal deformation or thermal deterioration of the plastic container.

  Furthermore, the plasma CVD film forming apparatus according to the present invention has a space for accommodating a plastic container, and the plastic container is placed in the space so that the gas inside the container and the gas outside the container do not cross each other. An external electrode that also serves as a vacuum chamber that can be housed in an internal electrode, an internal electrode that is insulated from the external electrode and is removably disposed inside the plastic container, and a source gas or a discharge gas for plasmatization A container internal gas introduction means for introducing the container internal gas into the plastic container, and a container external gas introduction means for introducing the container external gas, which is a raw material gas or a discharge gas for plasmatization, into the space, High-frequency supply means for supplying a high frequency to the external electrode, and at least an inner surface or an outer surface of the plastic container 2 is a plasma CVD film forming apparatus for forming a CVD film on either one of the above materials, wherein the entire surface or a part of the surface of the internal electrode is made of a material having a larger secondary electron emission coefficient than the electrode material of the internal electrode. A secondary electron emission layer is provided. Many secondary electrons are emitted from the secondary electron emission layer to the gas inside the container, and as a result, the plasma density of the gas inside the container is increased. As a result, it is possible to increase the deposition rate without causing the plastic container to undergo thermal deformation or thermal deterioration.

  The plasma CVD film forming apparatus according to the present invention has a space that can accommodate a plastic container, and is inserted into and removed from the inside of the plastic container in an insulated state from the external electrode that also serves as a vacuum chamber. An internal electrode that can be arranged, a container internal gas introduction means for introducing a raw material gas for plasmatization into the plastic container, and a high frequency supply means for supplying a high frequency to the external electrode, the plastic In the plasma CVD film forming apparatus for forming a CVD film on the inner surface of the container, the entire surface of the internal electrode or a part of the surface is formed of a secondary material having a secondary electron emission coefficient larger than that of the electrode material of the internal electrode. An electron emission layer is provided. Also in this apparatus, since the secondary electron emission layer is provided on the entire surface of the internal electrode or a part of the surface, many secondary electrons are transferred from the secondary electron emission layer to the plasma source gas inside the container. As a result, the plasma density of the source gas increases. As a result, it is possible to increase the deposition rate without causing the plastic container to undergo thermal deformation or thermal deterioration.

  In the plasma CVD film forming apparatus, it is preferable that magnetic field generating means such as an induction coil or a permanent magnet is provided around the outer wall surface of the external electrode. By providing magnetic field generating means such as induction coils and permanent magnets on the outer wall surface of the external electrode, the plasma density can be increased.

  As described above, in an apparatus for forming a CVD film on at least one of the inner surface and the outer surface of a plastic container, the film formation speed is increased and the film density is increased by increasing the plasma density of the plasma gas. Can be realized. Due to the densification of the film, the gas barrier property of the plastic container is improved.

Hereinafter, although an embodiment is shown and explained in detail about the present invention, the present invention is limited to these descriptions and is not interpreted. 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.
(Embodiment of simultaneous plasma ignition type apparatus inside and outside the container)

  FIG. 1 is a conceptual diagram showing the relationship of the basic configuration of the first embodiment of the CVD film forming apparatus according to the present embodiment. The CVD film forming apparatus according to the present embodiment has a void 80 that accommodates the plastic container 7, an external electrode 3 that also serves as a vacuum chamber, and an internal electrode 9 that is detachably disposed inside the plastic container 7. A lid 5 for supporting the internal electrode 9, a container internal gas introduction means 41, a container external gas introduction means 38, an external electrode 3 is provided with high frequency supply means 39 for supplying a high frequency. A film forming chamber 6 is constituted by the external electrode 3 and the lid 5 to form a sealable vacuum chamber.

  A space 80 is provided inside the external electrode 3, and this space is a storage space for storing a plastic container 7 to be coated, for example, a PET bottle which is a container made of polyethylene terephthalate resin. Here, in the present embodiment, it is preferable that the inner wall of the void 80 of the external electrode 3 has a shape having a portion separated from the outer surface of the plastic container 7 when the plastic container 7 is accommodated. The wall surface of the void 80 and the outer surface of the container may be partially separated, or the entire surface may be separated. In the conventional apparatus exemplified by the apparatus of Patent Document 1, when the self-bias voltage is applied to the inner surface of the container, the wall surface of the void 80 and the outer surface of the container must be brought close to each other. Then, means for transmitting a high frequency to the container wall surface is provided so that a self-bias voltage is applied to the container wall surface without bringing them close to each other. As will be described later, this means is to generate plasma outside the container in the void 80 and use the plasma as a conductor. The reason why the self-bias voltage is applied to the wall surface of the container is to cause ions of plasma source gas to collide with the wall surface of the container to form a dense CVD film.

In the present embodiment, the gap between the wall surface of the void 80 and the outer surface of the container depends on the electrical conductivity of the plasma container external gas. For example, the height is 207 mm, the wall thickness is 0.3 mm, and the container capacity Is about ^{2 to} 50 mm in a carbonated round PET container (FIG. 2A type) having an inner surface area of 400 cm ² and a body diameter of 68.5 mm. This value largely depends on the high frequency output to be applied, the shape and size of the container, etc., and thus does not limit the present invention. However, in a conventional CVD film forming apparatus that does not introduce plasmaized container external gas, for example, an apparatus described in Patent Document 1, when forming a film in a similar container, the wall surface of the void 80 of the container and the outer surface of the container The gap needs to be approximately 1 mm or less. This must be ensured over the entire outer surface of the container. In the CVD film forming apparatus according to the first embodiment, for example, a gap can be eliminated in the container body and a gap can be provided in the shoulder. That is, the wall shape of the void 80 does not need to be similar to the outer shape of the container, and the void 80 can have a comprehensive shape that can accommodate containers of various shapes.

  In the CVD film forming apparatus according to the first embodiment, when the plastic container 7 is accommodated in the void 80, the wall surface shape or plastic that contacts the wall surface shape of the void 80 along the shapes of the bottom portion and the trunk portion of the plastic container 7. It is good also as a wall surface shape which touches along the shape of the bottom part of the container 7. FIG. In the CVD film forming apparatus according to the first embodiment, a plurality of plastic containers may be accommodated in the empty space 80.

  In the CVD film forming apparatus according to the first embodiment, secondary electron emission made of a material having a larger secondary electron emission coefficient than the electrode material of the external electrode is formed on the entire wall surface of the void 80 of the external electrode 3 or a part of the wall surface. It is preferable to provide the layer 81. The film thickness of the secondary electron emission layer 81 is preferably 10 nm to 50 μm. If it is less than 10 nm, the amount of secondary electron emission decreases. The upper limit is set to 50 μm in order to extend the life by forming a thicker film in consideration of the generation of etching by argon gas. Therefore, the secondary electron emission layer may be formed to a thickness greater than this, or may be regenerated by recoating. The plasma contacts the secondary electron emission layer 81, and secondary electrons are emitted from the secondary electron emission layer 81 into the plasma. At this time, even when the secondary electron emission layer 81 is not provided, secondary electrons are emitted from the wall surface of the empty space, but the amount thereof is small. By providing the secondary electron emission layer 81, electrons are easily emitted, and the plasma density is increased. The external electrode is formed of an electrode material such as stainless steel or aluminum. The plasma conductivity σ is proportional to the electron charge (e squared) and the electron density (Ne), and inversely proportional to the electron mass (Mc) and the collision frequency (v). Therefore, the conductivity of the gas also increases due to the increase in plasma density. Therefore, the sheath thickness generated near the outer surface of the external electrode and the container is reduced. As a result, the capacitance of the sheath increases, and the voltage drop between the outer electrode and the sheath can be reduced. As a result, the self-bias voltage applied to the inner surface of the bottle can be increased. As a result, a dense film is formed, and the gas barrier property is improved.

Examples of the material of the secondary electron emission layer 81 include 2A group alkaline earth metal oxides such as BeO, MgO, CaO, SrO, and BaO, 4A group metal oxides such as TiO ₂ and ZrO ₂ , and 2B such as ZnO. group metal-based _oxide, 3A group metal oxide such as _{Y 2 O 3, Al 2 O} 3, Ga 3B group metal oxides, such as _{2 O 3, SiO 2, PbO} 2, 4B group metal such as PbO Oxides, 3B group nitrides such as AlN, 3B group nitrides such as GaN and SiN, barium oxynitrides, fluorides such as LiF, MgF, and CaF, carbides such as SiC, diamond, carbon nanotubes, A carbon-based material such as DLC is used alone or in combination. These compounds may be used. In the MgO system, MgO—Al ₂ O ₃ , MgO—TiO ₂ , MgO—ZrO ₂ , MgO—V ₂ O ₅ , MgO—ZnO, MgO—SiO ₂ , MgO—SiO ₂ —TiO ₂ , MgO—RuO, MgO -MnOx, MgO-Cr ₂ O ₃ and the like. In the BaO system, BaTiO ₃ can be exemplified. Further, a small amount of a rare earth oxide such as NbO, LaO ₂ or SeO ₂ may be added to the material of the secondary electron emission layer. The secondary electron emission layer is formed by a film formation method such as MOCVD, sputtering, thermal spraying, sol-gel method, etc., with the wall surface of the void 80 of the external electrode as the film formation target.

  Although FIG. 1 illustrates the case where the external electrode 3 is provided on the entire wall surface of the space 80, it may be a part of the wall surface. When the secondary electron emission layer 81 is coated on a part of the wall surface, it can be exemplified as follows. In order to form a thicker CVD film on the bottom of the container than on other places, coating may be performed on the vicinity of the bottom of the plastic container 7 on the wall surface of the space 80. In addition, in order to form a thicker CVD film on the container body than in other places, the vicinity of the body of the plastic container 7 may be coated on the wall surface of the space 80. Alternatively, a pattern may be formed in a striped pattern in which lines are arranged over the entire wall surface of the void 80. By adjusting the line width and line interval, the area ratio between the coated surface and the non-coated surface can be optimized, and the plasma density can be increased without impeding the ignition of the plasma discharge. Further, the coating may be performed in a sea island shape, and the same area adjustment is possible by adjusting the diameter and interval of the islands. You may coat in the shape of a dot. Further, a striped, sea-island or dot-like coating may be applied to the vicinity of the bottom or the body of the plastic container 7 on the wall surface of the void 80. When the secondary electron emission layer 81 is coated on a part of the wall surface, it is preferable to coat an area of 30 to 70%.

  As described above, by providing the secondary electron emission layer 81 on the wall surface of the void 80, the plasma density increases as compared with the case where the secondary electron emission layer is not provided, so that the same gas flow rate, the same gas pressure, By increasing the self-bias voltage with the same high-frequency output, a dense CVD film is formed, and the gas barrier property is improved.

  In this embodiment, a permanent magnet 50 may be provided around the outer wall surface of the external electrode 3 as shown in FIG. Alternatively, as shown in FIG. 4, an induction coil 51 (the current supply means of the induction coil is not shown) may be provided around the outer wall surface of the external electrode 3. It is preferable to increase the plasma density outside the container in the void 80 by providing a magnetic field generating means such as an induction coil or a permanent magnet shown in FIG. By increasing the plasma density due to the circumferential arrangement of the magnetic field generating means, it is possible to ensure plasma ignition outside the container and to stabilize the gas outside the container as a conductor.

  Note that a trigger (not shown) may be installed in the external electrode 3 to forcibly perform plasma ignition.

  The accommodation space in the external electrode portion 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 reason why the external electrode 3 is divided into the upper external electrode 2 and the lower external electrode 1 is to easily mount and remove the container 7. That is, the lower external electrode 1 is removed from the upper external electrode 2, and the container 7 is attached and taken out from below the upper external electrode 2. Each electrode secures a sealing property with an O-ring 8 or the like interposed therebetween. The external electrode 3 may be divided into three or more. Further, the external electrode 3 may not be divided. In the case where the container 7 is not divided, the container 7 can be mounted and taken out from the opening 53 of the external electrode 3.

  The opening 53 of the external electrode 3 is provided with a lid 5 that plays a role of introducing a source gas into the plastic container 7 and supporting the internal electrode 9. When the plastic container 7 is accommodated in the void 80, it is preferable to provide the opening 53 so that the lid is positioned near the container mouth. The opening 53 is covered with a lid 5 to seal the film forming chamber 6. At this time, the lid 5 and the external electrode 3 ensure a sealing property with, for example, an O-ring 54 interposed therebetween.

  In addition, the lid 5 is provided with an opening 52 for the mouth that contacts the mouth of the plastic container 7. An O-ring 55 is provided at a location where the mouth opening 52 and the mouth of the plastic container 7 are in contact. When the plastic container 7 is received, the container of the plastic container 7 is bordered by the mouth of the plastic container 7. Make sure that the internal gas and the container external gas do not cross each other. Further, the plastic container 7 is brought into contact with the mouth opening 52 through an insulator so that electrons that generate a self-bias voltage on the wall surface of the plastic container 7 are not grounded during plasma discharge. In the CVD film forming apparatus according to the first embodiment, in order to realize an insulating state, for example, the lid 5 is constituted by the conductive member 4b and the insulating members 4a and 10 so that the insulating member 4a and the plastic container are in contact with each other. The lid 5 supports the internal electrode 9 so that the internal electrode 9 penetrates the opening 52 for the mouth. When the internal electrode 9 is supported, the lid 5 insulates the internal electrode 9 and the external electrode 3 from each other. In the present embodiment, in order to realize the insulation state, for example, the insulating member 4 a of the lid 5 is in contact with the opening 53 of the external electrode 3, and the insulating member 10 of the lid 5 is in contact with the internal electrode 9.

  The lid 5 is provided with a mouth opening 52 connected to the void 80 in the external electrode 3, and a space 23 is provided inside the lid 5. The internal electrode 9 is inserted into the space 80 in the external electrode 3 from above the conductive member 4b through the space 23 in the conductive member 4b, the opening portion 52 of the conductive member 4b and the insulating member 4a. The proximal end of the internal electrode 9 is disposed on the insulating member 10. On the other hand, the tip of the internal electrode 9 is disposed inside the plastic container 7. The lid 5 is provided with a container support 56 for supporting and fixing the plastic container 9 in an electrically insulated state. The container support 56 may be a floating potential.

  The internal electrode 9 has a tubular shape whose inside is hollow, and is disposed in the plastic container 7 so as to be insertable / removable. At this time, in order to generate plasma discharge inside the plastic container 7, the internal electrode 9 is preferably not in contact with the inner surface of the plastic container 7. As shown in FIG. 1, when the plastic container 7 is mounted in the film forming chamber 6, the internal electrode 9 is disposed in the external electrode 3 and is disposed in the plastic container 7. A gas blowing port 49 is provided at the tip of the internal electrode 9. Further, the internal electrode 9 is preferably grounded. Examples of the material of the internal electrode 9 include stainless steel (SUS304) and aluminum. Furthermore, the inner diameter of the internal electrode 9 is preferably 1.5 mm or less, more preferably 1.0 mm or less in order to prevent plasma generation inside the tube of the internal electrode. By setting the inner diameter to 1.5 mm or less, it is possible to suppress the occurrence of electrode contamination inside the tube of the internal electrode. Further, the thickness of the internal electrode is preferably 1 mm or more in order to ensure mechanical strength.

  Here, it is preferable to provide a secondary electron emission layer 82 made of a material having a larger secondary electron emission coefficient than the electrode material of the internal electrode 9 on the entire surface or a part of the surface of the internal electrode 9. The film thickness of the secondary electron emission layer 82 is preferably 10 nm to 50 μm. If it is less than 10 nm, the amount of secondary electron emission decreases. The upper limit is set to 50 μm in order to extend the life by forming a thicker film in consideration of the generation of etching by argon gas. Therefore, the secondary electron emission layer may be formed to a thickness greater than this, or may be regenerated by recoating. The plasma generated in the plastic container 7 contacts the secondary electron emission layer 82, and secondary electrons are emitted from the secondary electron emission layer 82 into the plasma. At this time, even when the secondary electron emission layer 82 is not provided, secondary electrons are emitted from the surface but the amount thereof is small. By providing the secondary electron emission layer 82, electrons are easily emitted, and the plasma density is increased. Thereby, the film forming speed is increased.

  The material of the secondary electron emission layer 82 is the same as the material of the secondary electron emission layer 81. The secondary electron emission layer 82 is formed by a film formation method such as an MOCVD method, a sputtering method, thermal spraying, or a sol-gel method using the outer surface of the internal electrode as a film formation target.

  Although FIG. 1 shows a case where only the portion where the internal electrode 9 is inserted into the container is shown, the entire surface may be coated. When the secondary electron emission layer 82 is coated on a part of the surface, the following can be exemplified in addition to the case where the container insertion portion is coated. The entire surface of the internal electrode 9 may be formed in a striped pattern in which lines are arranged. By adjusting the line width and line interval, the area ratio between the coated surface and the non-coated surface can be optimized, and the plasma density can be increased without impeding the ignition of the plasma discharge. Further, the coating may be performed in a sea island shape, and the same area adjustment is possible by adjusting the diameter and interval of the islands. You may coat in the shape of a dot. Further, a striped, sea-island or dot-like coating may be applied to the insertion portion of the container. When the secondary electron emission layer 82 is coated on a part of the surface, it is preferable to coat an area of 10 to 40%.

  As described above, by providing the secondary electron emission layer 82 on the surface of the internal electrode, the plasma density is increased as compared with the case where the secondary electron emission layer is not provided. Therefore, the same gas flow rate, the same gas pressure, and the same The film forming speed is increased by the high frequency output.

  In FIG. 1, the case where the secondary electron emission layer is provided on both the container insertion portion and the entire wall surface of the cavity 80 of the external electrode 3 on the surface of the internal electrode 9 is illustrated. good.

  In the case where the secondary electron emission layer is an alkaline earth metal oxide such as MgO, a dry air blowing means for blowing the secondary electron emission layer with dry nitrogen gas while the film formation chamber 6 is opened to the atmosphere. (Not shown) is preferably provided.

  The container according to the present embodiment 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 in the plastic container according to the present embodiment include beverages such as carbonated beverages, fruit juice beverages, and soft drinks, as well as pharmaceuticals, agricultural chemicals, and dry foods that dislike moisture absorption.

  In the present embodiment, a container having a high degree of freedom in shape can be employed including the container shape illustrated in FIG. The bottom, trunk, shoulder and neck of the container will be referred to together with the container shape as shown in FIG. Therefore, these are not defined by the height of the container. The container may be provided with a reduced pressure absorption surface. When the reduced pressure absorption surface is provided, it is difficult to make the inner wall surface of the external electrode and the outer surface of the container completely adhere to each other. In the CVD film forming apparatus according to the first embodiment, since a gap may be provided between the wall surface of the void 80 and the outer surface of the container, it is suitable for forming a CVD film on a container having a reduced pressure absorption surface. .

  Resin used when molding the plastic container of this embodiment is polyethylene terephthalate resin (PET), polyethylene terephthalate copolyester resin (copolymer using cyclohexane dimethanol instead of ethylene glycol as the alcohol component of polyester) Eastman), 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, polyvinylidene chloride tree , Polyamide resin, polyamideimide resin, polyacetal resin, polycarbonate resin, polysulfone resin, or ethylene tetrafluoride resin, acrylonitrile - styrene resins, acrylonitrile - butadiene - styrene resin, can be exemplified. Among these, PET is particularly preferable.

  The container internal gas introduction means 41 introduces the container internal gas supplied from the container internal gas generation source 20 into the plastic container 7. That is, one side of the pipe 11 is connected to the base end of the internal electrode 9, and the other side of the pipe 11 is connected to one side of the mass flow controller 19 via the vacuum valve 16. The other side of the mass flow controller 19 is connected to a container internal gas generation source 20 via a pipe 22. The container internal gas generation source 20 generates a raw material gas or a discharge gas for making it into plasma.

  The source gas is selected as the container internal gas when a CVD film is formed on the inner surface of the plastic container. 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, especially ethylene hydrocarbons such as ethylene, propylene or butylene, or acetylene hydrocarbons such as acetylene, arylene or 1-butyne from the viewpoint of hygiene 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 embodiment 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.

  On the other hand, the discharge gas is selected as a container internal gas when the inner surface of the plastic container 7 is subjected to plasma surface modification. A gas to be converted into plasma is selected in the same manner as the source gas. The discharge gas is preferably a rare gas such as helium or argon, nitrogen, oxygen, carbon dioxide, fluorine, water vapor gas, ammonia gas, carbon tetrafluoride, or a mixed gas thereof among the gases to be converted into plasma.

  The container external gas introduction means 38 is for introducing a raw material gas or a discharge gas into the outside of the plastic container 7 and into a sealed space in the space 80 (hereinafter referred to as “container outside”). The container external gas introduction means 38 introduces the container external gas supplied from the container external gas generation source 37. That is, a container external gas introduction port (not shown) is provided at a predetermined position of the lid 5 or the external electrode 3 through which gas can be introduced outside the container in the film forming chamber 6. In the case of FIG. 1, a case where a container external gas introduction port is provided in the lid 5 is shown. Starting from the container external gas inlet provided in the lid 5 or the external electrode 3, one side of the pipe 33 is connected, and the other side of the pipe 33 is connected to one side of the mass flow controller 35 via the vacuum valve 34. ing. The other side of the mass flow controller 35 is connected to a container external gas generation source 37 via a pipe 36. The container external gas generation source 37 generates a raw material gas or a discharge gas for making it into plasma.

  Since the gas outside the container is a raw material gas or a discharge gas that is turned into plasma, it is turned into plasma outside the container that is a sealed space by the high frequency supplied to the external electrode 3. Since the containerized gas outside the plasma is a conductor, a high frequency is conducted to the outer surface of the plastic container 7. Due to the high frequency conducted to the wall surface of the plastic container 7, a potential difference is generated between the wall surface and the internal electrode 9, and the gas inside the container is turned into plasma inside the plastic container 7.

  Since the gas inside the container and the gas outside the container do not cross each other, the plasma is ignited independently from the inside of the container and the outside of the container which is a sealed space.

  The source gas is selected as a container external gas when a CVD film is formed on the outer surface of the plastic container. As the source gas, the same type of gas as that of the source gas of the container internal gas is selected.

  On the other hand, the discharge gas is selected as a container external gas when the outer surface of the plastic container 7 is subjected to plasma surface modification. A gas to be converted into plasma is selected in the same manner as the source gas. As the discharge gas, the same type of gas as that of the discharge gas of the container external gas is selected.

  The space 23 in the conductive member 4 b is connected to one side of the pipe 13, and the other side of the pipe 13 is connected to the vacuum pump 21 via the vacuum valve 18. This vacuum pump 21 is connected to an exhaust duct 29. The space 23 in the conductive member 4 b is connected to one side of the pipe 12, and the other side of the pipe 12 is connected to a leak source 27 for opening the inside of the container to the atmosphere via the vacuum valve 17.

  In order to open the outside of the container, which is a sealed space, to the atmosphere, the external electrode 3 is connected to one side of the pipe 30, and the other side of the pipe 30 is connected to the leak source 32 via the vacuum valve 31. Further, the outside of the container, which is a sealed space, is connected to one side of the pipe 45, and the other side of the pipe 45 is connected to the vacuum pump 25 via the vacuum valve 40. This vacuum pump 25 is connected to an exhaust duct 26.

  The high-frequency supply means 39 includes an automatic matching unit (matching box) 14 connected to the external electrode 3 and a high-frequency power source 15 connected to the automatic matching unit 14 via a coaxial cable. The high frequency power supply 15 is grounded.

  The high frequency power supply 15 generates a high frequency which is energy for converting the container external gas and the container internal gas into plasma. In order to perform matching quickly and reduce the time required for plasma ignition, it is preferably a transistor type high frequency power source and a frequency movable type or a high frequency power source that performs electronic matching. 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. For example, a high frequency output of 10 to 2000 W is selected.

  The automatic matching unit 14 adjusts the impedance of the internal electrode 9 and the film forming chamber 6 so as to match with the inductance L and the capacitance C.

  FIG. 5 shows a CVD film forming apparatus according to the second embodiment. The apparatus of FIG. 5 is an example in which an external electrode 62 composed of an upper external electrode 60 and a lower external electrode 61 is used as a film forming chamber. In this case, unlike the embodiment, no lid is provided. That is, as long as the external electrode 62 and the internal electrode 9 are insulated, the shape of the film forming chamber can be variously changed. The lower external electrode 61 is supported by an elevating means 65, and the external electrode 62 (deposition chamber) can be freely opened and closed by raising and lowering the lower external electrode 61.

  Next, a method for manufacturing a CVD film-coated plastic container using the CVD film forming apparatus according to the first embodiment will be described. The outside of the container in the film forming chamber 6 is opened to the atmosphere by opening the vacuum valve 31. The inside of the plastic container 7 is opened to the atmosphere by opening a vacuum valve 17. Further, the lower external electrode 1 of the external electrode 3 is removed from the upper external electrode 2. The uncoated 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, after the vacuum valve 17 is closed, the vacuum valve 18 is opened and the vacuum pump 21 is operated. As a result, the inside of the plastic container 7 is exhausted through the pipe 13 to be evacuated. The pressure in the plastic container 7 at this time is 2.6 to 66 Pa. Simultaneously with this operation, the vacuum valve 31 is closed, the vacuum valve 40 is opened, and the vacuum pump 25 is operated. As a result, the inside of the container, which is a sealed space, is evacuated through the pipe 45 to become a vacuum. The pressure inside the container at this time is 2.6 to 66 Pa.

  Next, the vacuum valve 16 is opened, the container internal gas generation source 20 generates the container internal gas, the container internal gas is introduced into the pipe 22, and the container internal gas whose flow rate is controlled by the mass flow controller 19 is supplied to the pipe 11 and The gas is blown out from the gas outlet 49 through the internal electrode 9 at the ground potential. Thereby, the gas inside the container is introduced into the plastic container 7. The inside of the plastic container 7 is maintained and stabilized at a pressure suitable for converting the gas inside the container into plasma, for example, about 6.6 to 665 Pa, by controlling the balance between the gas flow rate and the exhaust capacity. Simultaneously with this operation, the vacuum valve 34 is opened, the container external gas generation source 37 generates the container external gas, the container external gas is introduced into the pipe 36, and the container external gas whose flow rate is controlled by the mass flow controller 35 is The air is blown out from the container external gas inlet (not shown) through the pipe 33 into the outside of the container which is a sealed space. As a result, the gas outside the container is introduced into the outside of the container. Then, the inside of the container is maintained at a pressure suitable for turning the container outside gas into plasma, for example, about 6.6 to 665 Pa, and is stabilized by the balance between the controlled gas flow rate and the exhaust capacity. The flow rates of the container internal gas and the container external gas differ depending on the capacity of the container, but are, for example, 50 to 500 sccm.

  Next, a high frequency output is supplied to the external electrode 3 to make the container internal gas and the container external gas into plasma almost simultaneously, and a DLC film is formed on at least one of the inner surface and the outer surface of the plastic container. That is, an RF output (for example, 13.56 MHz) is supplied to the external electrode 3 by the high frequency supply means 39. The high frequency output is, for example, 10 to 2000 W. Thereby, plasma is ignited between the external electrode 3 and the internal electrode 9. At this time, although the inside of the plastic container 7 and the outside of the container form separate spaces with the wall surface of the plastic container as a boundary, plasma is ignited in both. That is, plasma is generated outside the container by the high frequency supplied to the external electrode 3, and the high frequency is guided to the wall surface of the plastic container 7 using the plasmaized container external gas as a conductor, and the container internal gas is also converted into plasma inside the plastic container 7. Is done. At this time, the automatic matching unit 14 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. As a result, hydrocarbon-based plasma is generated in the space filled with the source gas, and a DLC film is formed on at least one of the inner surface and the outer surface of the plastic container 7. At this time, the secondary electron emission layers 81 and 82 are exposed to the plasma to emit secondary electrons, and both the plasma density outside the container and the plasma density inside the container increase. As the plasma density outside the container increases, a high self-bias voltage is applied to the wall surface of the plastic container. The film formation rate is high and the film becomes dense. At this time, the increase in the plasma density inside the container contributes to an increase in the deposition rate. When the secondary electron emission layer is provided (for example, 200 to 500 liters / second), the film formation rate is 2 to 2 compared with the case where the secondary electron emission layer is not provided (for example, 100 liters / second). It was improved 5 times. The film formation time at this time is as short as several seconds. Next, the RF output from the high frequency supply means 39 is stopped, the plasma is extinguished, and the film formation of the DLC film is completed. At substantially the same time, the vacuum valve 16 and the vacuum valve 34 are closed to stop the supply of the gas inside the container and the gas outside the container.

  Next, in order to remove the container internal gas or the container external gas remaining inside and outside the plastic container 7, the vacuum valves 18 and 40 are opened, and these gases are exhausted by the vacuum pumps 21 and 25. Thereafter, the vacuum valves 18 and 40 are closed, and the exhaust is finished. At this time, the pressure inside the plastic container 7 and inside the container is 6.6 to 665 Pa, respectively. Thereafter, the vacuum valves 17 and 31 are opened. As a result, air enters the space 23 in the lid 5 and the inside of the plastic container 7, and in parallel, air enters the space inside the container and the inside of the film forming chamber 6 is opened to the atmosphere.

  Next, the lower external electrode 1 of the external electrode 3 is removed from the upper external electrode 2. The plastic container 7 accommodated in the space inside the upper external electrode 2 is taken out from the lower side of the upper external electrode 2. The lid 5 and the external electrode 3 may be removed and the plastic container 7 attached to the external electrode 3 may be removed.

Next, in the apparatus of the present embodiment, a specific form in the case where a raw material gas or a discharge gas is selected as the container external gas and the container internal gas will be described. In the present embodiment, there are three combinations of selection of the container external gas and the container internal gas. This is shown in Table 1.

  In gas combination 1, a CVD film can be formed on the inner surface of the container, while the outer surface can be subjected to plasma surface modification. In particular, when the source gas mentioned above, for example, acetylene gas, is used as the source gas, a dense DLC film having gas barrier properties can be formed on the inner surface of the plastic container. By forming a DLC film on the inner surface of the container, it is possible to provide gas barrier properties such as oxygen and carbon dioxide and water vapor barrier properties, and to further suppress adsorption of fragrance components and the like on the container wall surface and sorption to the container resin. it can. On the other hand, the plasma surface modification of the outer surface of the container is as follows. That is, if a rare gas such as helium or argon, which is an inert gas, is used as the discharge gas for the container external gas, the outer surface of the plastic container is promoted to be roughened by inert plasma treatment, improving the adhesion of labels and the like, It is possible to improve printability and prevent static electricity (prevention of dirt). By using hydrogen, oxygen, nitrogen, water vapor, ammonia gas, carbon tetrafluoride or a mixed gas thereof as the discharge gas, functional groups can be imparted by reactive plasma treatment to improve the adhesion of labels and the like. . Therefore, different functions can be separately imparted to the inner surface of the container and the outer surface of the container.

  In the gas combination 2, a CVD film can be formed on the outer surface of the container, while the inner surface can be subjected to plasma surface modification. When the source gas mentioned above, for example, acetylene gas, is used as the source gas, a DLC film can be formed on the outer surface of the container. The gas barrier property can be secured by the DLC film formed on the outer surface of the container. Furthermore, it is possible to realize a reduction in the static friction coefficient and prevent external scratches. On the other hand, the plasma surface modification of the inner surface of the container is as follows. That is, when helium, argon, oxygen, nitrogen or the like is used as the discharge gas for the container internal gas, sterilization of microorganisms can be achieved. This bactericidal action is not only due to plasma active species, but also due to ultraviolet rays emitted from plasma. By using nitrogen, oxygen, carbon dioxide, fluorine or a mixed gas thereof as the discharge gas, polarity by reactive plasma treatment can be introduced to improve the wettability of the inner surface of the container.

In the gas combination 3, a CVD film can be formed on both the inner surface and the outer surface of the container. When the source gas mentioned above, for example, acetylene gas, is used as the source gas, a dense DLC film having gas barrier properties can be formed on the inner surface and the outer surface of the container. By forming a gas barrier DLC film on both wall surfaces of the plastic container, an ultra-high gas barrier plastic container can be manufactured. In addition, since the gas barrier property is secured on both wall surfaces, the thickness of the DLC film can be reduced, and the film formation time can be shortened. Further, since the DLC film is formed on the outer surface of the container, it is possible to reduce the static friction coefficient and prevent the outer surface scratches.
(Embodiment of plasma ignition type device only inside the container)

  FIG. 6 is a conceptual diagram showing the relationship of the basic configuration of the third embodiment of the CVD film forming apparatus according to this embodiment. The CVD film forming apparatus according to the present embodiment has a void 80 that can accommodate the plastic container 7, and is inserted into the plastic container 7 while being insulated from the external electrode 3 that also serves as a vacuum chamber and the external electrode 3. An internal electrode 9 that is detachably disposed, a container internal gas introduction means 41 that introduces a raw material gas to be converted into plasma into the plastic container 7, and a high frequency supply means 39 that supplies a high frequency to the external electrode 3. Prepare. A film forming chamber 6 is constituted by the external electrode 3 and the lid 5 to form a sealable vacuum chamber. Since the CVD film forming apparatus according to the third embodiment is an apparatus of a type that does not introduce a container external gas as a plasma conductor, the wall surface of the void 80 of the external electrode 3 is formed in the plastic container 7 when the plastic container 7 is accommodated. Similar shape almost in contact with the outer surface.

  In the CVD film forming apparatus according to the third embodiment, a permanent magnet or an induction coil may be provided around the outer wall surface of the external electrode 3 as in the apparatus according to the first embodiment shown in FIGS. Thus, it is preferable to increase the plasma density inside the container.

  As in the first embodiment, the external electrode 3 has a structure divided into an upper external electrode 2 and a lower external electrode 1, and a lid 5 is provided to ensure insulation between the internal electrode 9 and the external electrode 3. Is formed of an insulating member. The internal electrode 9 is supported by the insulating member 10. Further, the internal electrode 9 is inserted into the space 80 of the external electrode 3 through the space 23 and the mouth opening 52 provided in the lid 5. The tip of the internal electrode 9 is arranged inside the plastic container 7 accommodated in the space 80.

  The internal electrode 9 has the same configuration as that of the first embodiment, and secondary electrons made of a material having a larger secondary electron emission coefficient than the electrode material of the internal electrode 9 on the entire surface or a part of the surface of the internal electrode 9. An emission layer 82 is provided. As a result, the plasma density also increases in the CVD film forming apparatus according to the second embodiment. Thereby, the film forming speed is increased. The material, coating mode, and coating method of the secondary electron emission layer 82 are the same as those in the embodiment. In the case where the secondary electron emission layer is an alkaline earth metal oxide such as MgO, a dry air blowing means for blowing the secondary electron emission layer with dry nitrogen gas (non-air) while the film formation chamber 6 is opened to the atmosphere (Shown) is preferably provided.

  The container internal gas introduction means 41 has the same configuration as that of the first embodiment, and the same raw material gas as that of the first embodiment is supplied into the container. The high frequency supply means 39, the exhaust pipe 13, the vacuum pump 21, and the exhaust duct 29 constituting the exhaust system inside the container also have the same configuration as in the first embodiment.

  When manufacturing a CVD film-coated plastic container using the CVD film forming apparatus according to the third embodiment, a source gas is supplied only into the container, and the source gas is converted into plasma to form a film. The operation for generating plasma inside the container is the same as in the CVD film forming apparatus according to the first embodiment. When the secondary electron emission layer 82 is exposed to the plasma, secondary electrons are emitted, and the plasma density inside the container increases. This increases the deposition rate. When the secondary electron emission layer is provided (for example, 200 to 500 liters / second), the film formation rate is 2 to 2 compared with the case where the secondary electron emission layer is not provided (for example, 100 liters / second). It was improved 5 times.

  In 1st-3rd embodiment, although the PET bottle for drinks is used as a container which forms a thin film inside, it is also possible to use the container used for another use.

  In the first to third embodiments, the DLC film or the Si-containing DLC film is cited as the thin film formed by the CVD film forming apparatus. However, when forming another thin film in the container, the above film forming apparatus is used. It is also possible to use.

  The DLC film is formed to have a thickness of 0.003 to 5 μm.

It is a conceptual diagram which shows the 1st form of the CVD film-forming apparatus which concerns on this embodiment. It is a conceptual diagram which shows the specific shape of the plastic container which concerns on this embodiment, and shows 6 forms of (a)-(f). In the 1st form of a CVD film-forming apparatus, it is a conceptual diagram at the time of arranging a permanent magnet as a magnetic field generation means around an external electrode. In the first embodiment of the CVD film forming apparatus, the case where an induction coil is provided around the external electrode as a magnetic field generating means is shown. It is a conceptual diagram which shows the 2nd form of the CVD film-forming apparatus which concerns on this embodiment. It is a conceptual diagram which shows the 3rd form of the CVD film-forming apparatus which concerns on this embodiment.

Explanation of symbols

1, 61 Lower external electrode 2, 60 Upper external electrode 3, 62 External electrode 4a, 4c, 10 Insulating member 4b Conductive member 5 Lid 6 Film forming chamber 7 Plastic container 8, 53, 54, 55, 64 O-ring 9 Internal electrode 11, 12, 13, 22, 30, 33, 36, 45 Piping 14 Automatic matching device (matching box)
15 High frequency power supply (RF power supply)
16, 17, 18, 31, 34, 40 Vacuum valve 19, 35 Mass flow controller 20 Vessel internal gas generation source 21, 25 Vacuum pump 27, 32 Leak source 24, 28 Vacuum gauge 26, 29 Exhaust duct 37 Vessel external gas generation source 38 External gas introduction means 39 High frequency supply means 41 Internal gas introduction means 49 Gas outlet 50 Permanent magnet 51 Inductive coil
56 Container support
65 Lifting means
80 Void 81, 82 Secondary electron emission layer

Claims (5)

An external electrode also serving as a vacuum chamber having a space for accommodating a plastic container, and capable of accommodating the plastic container in the space so that the gas inside the container and the gas outside the container do not cross each other An internal electrode that is detachably disposed inside the plastic container in an insulated state from the external electrode, and introduces the container internal gas, which is a raw material gas or a discharge gas, to be converted into plasma into the plastic container A container internal gas introducing means, a container external gas introducing means for introducing the container external gas, which is a raw material gas or a discharge gas to be converted into plasma, into the void, and a high frequency supply means for supplying a high frequency to the external electrode; And a plasma C for forming a CVD film on at least one of the inner surface and the outer surface of the plastic container. A D film-forming apparatus,
A plasma CVD film-forming method, wherein a secondary electron emission layer made of a material having a secondary electron emission coefficient larger than that of the electrode material of the external electrode is provided on the entire wall surface of the void of the external electrode or a part of the wall surface apparatus.   2. The plasma CVD according to claim 1, wherein a secondary electron emission layer made of a material having a secondary electron emission coefficient larger than that of the electrode material of the internal electrode is provided on the entire surface of the internal electrode or a part of the surface. Deposition device. An external electrode also serving as a vacuum chamber having a space for accommodating the plastic container and capable of accommodating the plastic container in the space so that the gas inside the container and the gas outside the container do not intersect with each other The internal electrode disposed in the plastic container so as to be insertable / removable in an insulated state from the external electrode, and the container internal gas, which is a raw material gas or a discharge gas to be converted into plasma, is introduced into the plastic container. A container internal gas introducing means, a container external gas introducing means for introducing the container external gas which is a raw material gas or a discharge gas to be converted into plasma into the space, and a high frequency supply means for supplying a high frequency to the external electrode And plasma C for forming a CVD film on at least one of the inner surface and the outer surface of the plastic container A D film-forming apparatus,
A plasma CVD film forming apparatus, wherein a secondary electron emission layer made of a material having a secondary electron emission coefficient larger than an electrode material of the internal electrode is provided on the entire surface of the internal electrode or a part of the surface. An external electrode having a space that can accommodate a plastic container and also serving as a vacuum chamber; an internal electrode that is insulated from the external electrode and is detachably disposed inside the plastic container; Plasma CVD for forming a CVD film on the inner surface of the plastic container, the container internal gas introduction means for introducing the raw material gas into the plastic container, and the high frequency supply means for supplying a high frequency to the external electrode In the film forming apparatus,
A plasma CVD film forming apparatus, wherein a secondary electron emission layer made of a material having a larger secondary electron emission coefficient than an electrode material of the internal electrode is provided on the entire surface of the internal electrode or a part of the surface. 5. The plasma CVD film forming apparatus according to claim 1, wherein a magnetic field generating means such as an induction coil or a permanent magnet is provided around the outer wall surface of the external electrode.

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