WO2005035826A1 - Plasma cvd film-forming apparatus - Google Patents

Abstract

An apparatus for forming a CVD film on at least one of the inner surface and outer surface of a plastic container is disclosed wherein the plasma intensity is increased. The CVD film-forming apparatus is characterized in that a secondary electron emission layer is formed on the entire or a part of the wall of a space provided in an external electrode for housing a plastic container and the secondary electron emission layer is composed of a material having a secondary electron emission coefficient larger than that of the electrode material for the external electrode. It is further characterized in that a secondary electron emission layer is formed on the entire or a part of the surface of an internal electrode which is removably arranged within the container to be insulated with the external electrode and the secondary electron emission layer is composed of a material having a secondary electron emission coefficient larger than that of the electrode material for the internal electrode.

Description

 Specification

 Plasma CVD deposition equipment

 Technical field to which the invention belongs

The present invention relates to a method for coating at least one of an inner surface and an outer surface of a plastic container with a CVD film, particularly a DLC (diamond-like carbon) film, by a CVD (Chemical Vapor Deposition) method. The present invention relates to a plasma CVD film forming apparatus. Background art

 [0002] There is a disclosure of an invention of a vapor deposition apparatus using a CVD method, particularly a plasma CVD method, for vapor-depositing a DLC film on the inner surface of a plastic container for the purpose of improving gas barrier properties (for example, Patent Document 1). ;)). In Patent Document 1, the external electrode has a space almost similar in shape to the outer shape of the container to be housed. The reason why the outer wall of the plastic container is kept almost in contact with the outer wall surface of the outer electrode is to apply a self-bias voltage uniformly to the inner wall surface of the plastic container.

 [0003] If there is a space between the outer wall of the external electrode and the outer surface of the plastic container, the self-noise voltage is hard to be reduced at the separated portion of the inner wall of the plastic container. . Therefore, the source gas ions converted into plasma at the time of the plasma ignition do not strongly collide with the inner wall surface of the container, so that a dense DLC film cannot be obtained and the film quality becomes uneven. Furthermore, if the outer wall of the outer electrode and the outer surface of the plastic container are separated from each other over the entire surface, even if a self-bias voltage is not applied to the inner wall surface of the container and a uniform film is attached, the film is dense. It does not become a DLC film. Unless a dense DLC film can be obtained, sufficient gas nori properties cannot be obtained. Many irregularities such as heat-resistant containers, etc., make it impossible to completely contact the outer surface of the container and the wall surface of the empty space of the external electrode, making it difficult to achieve sufficient gas nobility.ヽ.

 Patent Document 1: JP-A-8-53117

 Disclosure of the invention

 Problems to be solved by the invention

[0005] If a high self-noise voltage can be applied to the inner wall surface of the container, the film becomes denser and As a result, it can be expected that the film will have good gas nolia 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, excessive supply of high frequency power causes thermal deformation and thermal degradation of the plastic container. Therefore, if the plasma density can be increased without increasing the supply of high-frequency power, the self-bias voltage can be increased without causing the above-described thermal deformation and thermal degradation. As a result, the film can be densified, which is advantageous. Also, by increasing the plasma density, it is possible to achieve a higher deposition rate.

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

 [0007] The present inventors have developed an apparatus for forming a CVD film on at least one of the inner surface and the outer surface of a plastic container, and have developed an entire wall surface or a wall surface of an external electrode housing a plastic container. By providing a secondary electron-emitting layer with a material strength that has a higher secondary electron emission coefficient than the electrode material of the external electrode, the plasma density of the plasma gas generated in the space outside the container in the cavity is increased. I found out that it can be done. In addition, a secondary electron emission that has a secondary electron emission coefficient larger than the electrode material of the internal electrode on the entire surface or a part of the surface of the internal electrode that serves as a ground electrode for the external electrode that supplies high-frequency power It has been found that the plasma density of the plasma gas generated inside the container can be similarly increased by providing the layer, and the present invention has been completed.

[0008] 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 formed so that the gas inside the plastic container and the gas outside the container do not intersect. An external electrode which also serves as a vacuum chamber capable of accommodating the above-mentioned space, an internal electrode which is detachably disposed inside the plastic container while being insulated from the external electrode, and a raw material gas for generating plasma. A container internal gas introducing means for introducing the container internal gas which is a discharge gas into the plastic container, and the container external gas which is a raw material gas for forming a plasma or a discharge gas. A container external gas introducing means for introducing into the empty space; and a high frequency supplying means for supplying high frequency to the external electrode, wherein a CVD film is formed on at least one of the inner surface and the outer surface of the plastic container. A plasma CVD film forming apparatus for forming a film, wherein a secondary electron emission layer having a material power having a larger secondary electron emission coefficient than the electrode material of the external electrode is formed on the entire wall surface or a part of the wall surface of the space of the external electrode. Is provided.

 [0009] In the external electrode of the CVD film forming apparatus of Patent Document 1, the wall shape of the cavity must be similar to the outer surface of the container. However, in the plasma CVD film forming apparatus according to the present invention, the wall shape of the empty space can be made freely as long as it can accommodate a plastic container. That is, by supplying the container external gas into the space created by the separation between the outer wall surface of the external electrode and the container outer surface and turning the container external gas into a plasma, the plasma outside the container when the CVD film is formed is formed. The gas becomes a conductor and conducts high-frequency waves to the outer surface of the container, so that the wall surface of the cavity comes into contact with the outer surface of the plastic container, and a state similar to that of the plastic container is generated. This makes it possible to apply a uniform self-bias voltage to the inner wall surface of the container. In other words, a uniform and dense CVD film can be formed on the container wall by introducing the gas outside the container. Thus, in a heat-resistant bottle having a reduced-pressure absorbing surface, a CVD film can be formed even if there is a gap between the wall surface of the space of the external electrode and the outer surface of the container. In addition, CVD films can be formed on plastic containers of various shapes without replacing one type of external electrode. Furthermore, this plasma CVD film forming apparatus selects a raw material gas or a discharge gas as the gas inside the container and the gas outside the container, respectively, so that only the inner surface of the container, only the outer surface of the container, or the inner surface of the container and the outer surface of the container. The CVD film can be formed on both surfaces. Furthermore, when the gas inside the container or the gas outside the container is used as the discharge gas, the plasma surface of the plastic container can be reformed with the plasma-generated discharge gas.

[0010] Here, in the plasma CVD film forming apparatus according to the present invention, a material having a higher secondary electron emission coefficient than the electrode material of the external electrode is formed on the entire wall surface or a part of the wall surface of the external electrode. A secondary electron emission layer is provided. As a result, many secondary electrons are emitted from the secondary electron emission layer toward the gas outside the container, and as a result, the plasma density of the gas outside the container can be increased. As a result, the self-built-up without thermal deformation and thermal degradation of the plastic container Negative voltage can be increased. As a result, densification of the film can be realized.

 Here, in the plasma CVD film forming apparatus according to the present invention, the entire surface or a part of the surface of the internal electrode is made of a material having a higher secondary electron emission coefficient than the electrode material of the internal electrode. It is preferable to provide a secondary electron emission layer. As a result, a large amount of secondary electrons are emitted from the secondary electron emission layer toward the gas inside the container and the gas outside the container, and as a result, the plasma density of the gas inside the container and the gas outside the container that are turned into plasma can be increased. it can. 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 and thermal deterioration of the plastic container. As a result, the film can be densified. In addition, an increase in the plasma density of the gas inside the container can realize a higher deposition rate without causing thermal deformation and thermal deterioration of the plastic container.

 [0012] Further, the plasma CVD film forming apparatus according to the present invention has a space for accommodating a plastic container, and the gas inside the plastic container and the gas outside the container do not intersect with each other. An external electrode which also serves as a vacuum chamber capable of accommodating the above-mentioned space, an internal electrode which is detachably disposed inside the plastic container in an insulated state with respect to the external electrode, and a raw material gas for generating plasma. Alternatively, a container internal gas introducing means for introducing the container internal gas which is a discharge gas into the plastic container, and introducing the container external gas which is a raw material gas for forming a plasma or a discharge gas into the space. A container external gas introducing means, and a high frequency supply means for supplying a high frequency to the external electrode, wherein an inner surface or an outer surface of the plastic container is provided. A plasma CVD film forming apparatus for forming a CVD film on at least one of the internal electrodes, wherein a material having a higher secondary electron emission coefficient than the electrode material of the internal electrode is formed on the entire surface or a part of the surface of the internal electrode. A secondary electron emission layer is provided. Many secondary electrons are emitted from the secondary electron emission layer toward the gas inside the container, and as a result, the plasma density of the gas inside the container that is turned into plasma increases. As a result, it is possible to increase the deposition rate without causing thermal deformation and thermal degradation of the plastic container.

[0013] Further, the plasma CVD film forming apparatus according to the present invention has a space capable of accommodating a plastic container, and has an external electrode serving also as a vacuum chamber, and the plastic container is insulated from the external electrode. Internal electrode that can be inserted and removed inside the A plasma CVD method comprising: a gas introduction means for introducing a feed gas into the plastic container; and a high frequency supply means for supplying a high frequency to the external electrode, wherein a CVD film is formed on the inner surface of the plastic container. In the film forming apparatus, a secondary electron emission layer having a material power having a larger secondary electron emission coefficient than the electrode material of the internal electrode is provided on the entire surface or a part of the surface of the internal electrode. I do. Also in this device, a secondary electron emission layer is provided on the entire surface of the internal electrode or on a part of the surface, so that a large amount of secondary electrons are emitted from the secondary electron emission layer to the raw material gas in the container. Is released, and as a result, the plasma density of the source gas increases. This makes it possible to increase the deposition rate without causing thermal deformation and thermal degradation of the plastic container.

In the plasma CVD film forming apparatus, it is preferable that 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. Induction coil on outer wall of external electrode

By arranging a magnetic field generating means such as a permanent magnet, the plasma density can be further increased.

 The invention's effect

 [0015] As described above, by increasing the plasma density of the plasma gas in an apparatus for forming a CVD film on at least one of the inner surface and the outer surface of the plastic container, the film forming speed is increased. And the densification of the film can be realized. Densification of the film improves the gas barrier properties of the plastic container.

 Brief Description of Drawings

FIG. 1 is a conceptual diagram showing a first embodiment of a CVD film forming apparatus according to the present embodiment.

 FIG. 2 is a conceptual diagram showing a specific shape of a plastic container according to the present embodiment, showing (a)-(f) six modes.

 FIG. 3 is a conceptual diagram in a case where a permanent magnet is provided around an external electrode as a magnetic field generating means in the first embodiment of the CVD film forming apparatus.

 FIG. 4 shows a case where an induction coil is provided around an external electrode as a magnetic field generating means in the first embodiment of the CVD film forming apparatus.

 FIG. 5 is a conceptual diagram showing a second embodiment of the CVD film forming apparatus according to the present embodiment.

FIG. 6 is a conceptual diagram showing a third embodiment of the CVD film forming apparatus according to the present embodiment. Explanation of reference numerals

 I, 61 Lower external electrode

 2, 60 Upper external electrode

 3, 62 External electrode

 4a, 4c, 10 Insulation material

4b conductive material

5 lid

 6 Deposition chamber

7 Plastic container

8,54,55,64 O-ring

9 Internal electrode

 I I, 12, 13, 22, 30, 33, 36, 45 Piping

14 Automatic matching box (matching box)

15 High frequency power supply (RF power supply)

 16, 17, 18, 31, 34, 40 Vacuum knob

19, 35 Mass flow controller

20 Gas source inside the container

 21, 25 Vacuum pump

 23 Lid interior space

 24, 28 vacuum gauge

 26, 29 Exhaust duct

 27, 32 leak source

 37 External gas source

38 External gas introduction means

39 High frequency supply means

 1 Means for introducing gas inside the container

 9 Gas outlet

0 permanent magnet 51 induction coil

 53 External electrode opening

 56 Container support

 65 Lifting means

 80 voids

 81, 82 Secondary electron emission layer

 BEST MODE FOR CARRYING OUT THE INVENTION

 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 descriptions. In addition, when members are common in the drawings, the same reference numerals are given. Hereinafter, embodiments of the present invention will be described with reference to FIGS.

 (Embodiment of Simultaneous Plasma Ignition Type Device Inside and Outside 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 space 80 for accommodating a plastic container 7, and has an external electrode 3 which also serves as a vacuum chamber and an internal electrode which is removably inserted into the plastic container 7. 9, a lid 5 that has an opening 52 for the mouth to which the mouth of the plastic container 7 is tightly closed, and supports the internal electrode 9, a container internal gas introducing means 41, a container external gas introducing means 38, A high frequency supply means 39 for supplying high frequency to the electrode 3. A film forming chamber 16 is composed of the external electrode 3 and the lid 5, and forms a vacuum chamber that can be sealed.

[0020] Inside the external electrode 3, a space 80 is provided, which is a space for accommodating a plastic container 7 to be coated, for example, a PET bottle which is a container made of polyethylene terephthalate resin. It is. Here, in the present embodiment, it is preferable that the inner wall of the space 80 of the external electrode 3 has a shape in which the outer surface force of the plastic container 7 is separated when the plastic container 7 is accommodated. The wall of the empty space 80 and the outer surface of the container may be separated from each other, or the entire surface may be separated. In a conventional device, such as the device of Patent Document 1, when applying a self-bias voltage to the inner surface of the container, the wall surface of the space 80 must be brought close to the outer surface of the container. In this configuration, the high frequency is transmitted to the container wall so that the self-bias voltage is applied to the container wall without bringing them close to each other. There is provided a means to make it work. As described below, this means is to generate plasma outside the container in the space 80 and use the plasma as a conductor. The reason why the self-bias voltage is applied to the wall of the container is to cause ions of the source gas converted into plasma to collide with the wall of the container to form a dense CVD film.

In the present embodiment, the gap between the wall surface of the space 80 and the outer surface of the container depends on the electric conductivity of the plasma-contained external gas of the container. For example, the height is 207 mm, the wall thickness is 0.3 mm, The container capacity is 500 ml, the inner surface area is 400 cm ² , and the volume of a carbonated round PET container (type of Fig. 2 (a)) with a body diameter of 68.5 mm is about 2-50 mm. This value is not limited to the present invention because it depends largely on the applied high-frequency output, the shape and size of the container, and the like. However, in a conventional CVD film forming apparatus that does not introduce a plasmaized gas outside the container, for example, an apparatus described in Patent Document 1, when forming a film in a similar container, the wall surface of the container cavity 80 and the outer surface of the container are not used. It is necessary to make the gap with lmm 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 a container body, and a gap can be provided in a shoulder. In other words, it is not necessary to make the wall shape of the space 80 similar to the outer shape of the container, and the space 80 can be formed into a comprehensive shape capable of accommodating containers of various shapes.

 In the CVD film forming apparatus according to the first embodiment, when the plastic container 7 is accommodated in the empty space 80, the wall shape of the empty space 80 contacts the shape of the bottom and the body of the plastic container 7. It may be a wall shape or a wall shape that is in contact with the shape of the bottom of the plastic container 7. Further, in the CVD film forming apparatus according to the first embodiment, the number of plastic containers housed in the space 80 may be plural.

In the CVD film forming apparatus according to the first embodiment, the material force having a higher secondary electron emission coefficient than the electrode material of the external electrode is applied to the entire wall or a part of the wall of the space 80 of the external electrode 3. It is preferable to provide a secondary electron emission layer 81! The thickness of the secondary electron emission layer 81 is preferably 1 Onm-50 m. If it is less than 10 nm, the amount of secondary electron emission decreases. The upper limit is set to 50 m in order to extend the life by forming a thicker layer taking into account the occurrence of etching by argon gas. Therefore, the secondary electron-emitting layer may be formed to have a thickness larger than that, or the layer may be re-coated and reproduced. Plasma contacts secondary electron emission layer 81 When touched, 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, the secondary electrons are emitted from the wall surface of the space, but the amount is small. By providing the secondary electron emission layer 81, electrons are easily emitted, and the plasma density is increased. The external electrodes are formed of an electrode material such as stainless steel or aluminum. Plasma conductivity _σ is proportional to electron charge (e squared) and electron density (Ne), and inversely proportional to electron mass (Mc) and collision frequency (V). Therefore, as the plasma density increases, the conductivity of the gas also increases. Therefore, the thickness of the outer electrode and the sheath generated near the outer surface of the container are reduced. As a result, the capacitance of the sheath increases, and the external electrode force can reduce the voltage drop between the sheaths. As a result, the self-bias voltage applied to the inner surface of the bottle can be increased, and as a result, a dense film is formed, so that the gas barrier property is improved.

 [0024] Materials for the secondary electron emission layer 81 include Group 2A alkaline earth metal-based oxides such as BeO, MgO, CaO, SrO, and BaO; Group 4A metal-based oxides such as TiO and ZrO; and ZnO. The 2B gold

 twenty two

 Group oxides, Group 3A metal oxides such as Y O, and Group 3B metal oxides such as Al O and Ga O

 2 3 2 3 2 3

 Material, 4B group metal oxide such as SiO, PbO, PbO, 3B group nitride such as A1N, GaN,

twenty two

 Use 3B group nitrides such as SiN, barium oxynitride, fluorides such as LiF, MgF and CaF, carbides such as SiC, and carbon-based materials such as diamond, carbon nanotubes, and DLC alone or in combination. . These compounds may be used. In the MgO system, MgO-Al O,

 twenty three

MgO—TiO, MgO—ZrO, MgO-VO, MgO-ZnO, MgO-SiO, MgO-SiO-

2 2 2 5 2 2

There are TiO, MgO-RuO, MgO-MnOx, MgO-CrO, etc. For BaO system, BaTiO

2 2 3 3 can be exemplified. In addition, rare earth acids such as NbO, LaO or SeO

 twenty two

 A small amount of a compound may be used. The secondary electron emission layer is formed by a film formation method such as a MOCVD method, a sputtering method, a thermal spraying, a sol-gel method, using the wall surface of the space 80 of the external electrode as a film formation target.

FIG. 1 illustrates a case where the secondary electron emission layer 81 is provided on the entire wall surface of the space 80 of the external electrode 3, but may be a part of the wall surface. When a part of the wall surface is coated with the secondary electron emission layer 81, the following can be exemplified. In order to deposit a thicker CVD film on the bottom of the container compared to other places, coat the wall of the empty space 80 near the bottom of the plastic container 7 You may. Further, in order to form a thicker CVD film on the body of the container as compared with other places, the wall of the space 80 may be coated near the body of the plastic container 7. Alternatively, a pattern may be formed in a stripe pattern in which lines are arranged over the entire wall surface of the space 80. By adjusting the line width and the line interval, the area ratio between the coated surface and the uncoated surface can be optimized, and the plasma density can be increased without preventing ignition of the plasma discharge. In addition, the same area can be adjusted by adjusting the diameter and spacing of the islands, which is good even if the coating is performed in a sea-island shape. It may be coated in a dot shape. Further, a stripe-shaped, sea-island-shaped or dot-shaped coating may be applied to the wall surface of the space 80 near the bottom of the plastic container 7 or near the trunk. When the secondary electron emission layer 81 is coated on a part of the wall surface, it is preferable to coat the area of 30 to 70%.

 As described above, by providing the secondary electron emission layer 81 on the wall surface of the space 80, the plasma density is increased as compared with the case where the secondary electron emission layer is not provided. Gas pressure • A dense CVD film is formed by increasing the self-noise voltage at the same high-frequency output, and the gas noria property is improved.

 In the present embodiment, as shown in FIG. 3, a permanent magnet 50 may be provided around the outer wall surface of the external electrode (reference numeral 3 in FIG. 1). Alternatively, as shown in FIG. 4, an induction coil 51 (current supply means of the induction coil is not shown) may be provided around the outer wall surface of the external electrode (reference numeral 3 in FIG. 1). It is preferable to increase the plasma density inside the space 80 outside the container by providing a magnetic field generating means such as an induction coil or a permanent magnet shown in FIG. 3 or FIG. By increasing the plasma density due to the peripheral arrangement of the magnetic field generating means, plasma ignition outside the container can be ensured, and the gas outside the container can be stabilized as a conductor.

 [0028] A trigger (not shown) may be provided in the external electrode 3 to force plasma ignition.

[0029] The accommodation space in 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 reason that 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 detached from the upper external electrode 2, and the lower force container 7 of the upper external electrode 2 is attached and taken out. Each electrode secures the sealing property with the O-ring 8 or the like interposed therebetween. In addition Alternatively, the external electrode 3 may be divided into three or more. Further, the external electrode 3 does not have to be divided. When not divided, the container 7 can be mounted and removed from the opening 53 of the external electrode 3.

 The opening 53 of the external electrode 3 is provided with a lid 5 that serves to introduce a raw material gas into the plastic container 7, support the internal electrode 9, and the like. When the plastic container 7 is stored in the empty space 80, the opening 53 is preferably provided so that the lid is located near the container opening. The opening 53 is covered with the lid 5 to seal the film forming chamber 16. At this time, the lid 5 and the external electrode 3 ensure sealing properties with the O-ring 54 or the like interposed therebetween.

 The lid 5 is provided with a mouth opening 52 to which the mouth of the plastic container 7 contacts. An O-ring 55 is provided at the place where the mouth opening 52 and the mouth of the plastic container 7 are in contact with each other. When the plastic container 7 is stored, the container of the plastic container 7 is separated from the mouth of the plastic container 7 The inner gas and the outer gas of the container are in close contact with each other so that they do not intersect. Furthermore, the plastic container 7 is in contact with the opening 52 for the mouth via an insulator so that the electrons that generate a self-bias voltage on the wall surface of the plastic container 7 during plasma discharge are not grounded. In the CVD film forming apparatus according to the first embodiment, in order to realize an insulating state, for example, the lid 5 is configured by the conductive member 4b and the insulating members 4a and 10 so that the insulating member 4a is in contact with the plastic container. You. The lid 5 supports the internal electrode 9 so that the internal electrode 9 passes through the mouth opening 52. When supporting the internal electrode 9, the lid 5 makes the internal electrode 9 and the external electrode 3 insulated. In the present embodiment, in order to realize an insulating state, for example, the insulating member 4a 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. .

[0032] The lid 5 is provided with a mouth opening 52 that is connected to a space 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 the upper part of the conductive member 4b through the space 23 in the conductive member 4b and the opening 52 of the conductive member 4b and the insulating member 4a. The base 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 arranged 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 have a floating potential. The internal electrode 9 has a tubular shape in which the inside also has a hollow force, and is arranged so as to be insertable / removable inside the plastic container 7. At this time, in order to generate a plasma discharge inside the plastic container 7, it is preferable that the internal electrode 9 is not in contact with the inner surface of the plastic container 7. As shown in FIG. 1, when the plastic container 7 is mounted on the film forming chamber 16, the internal electrode 9 is disposed inside the external electrode 3 and inside the plastic container 7. A gas outlet 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. Further, 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, the occurrence of electrode contamination inside the tube of the internal electrode can be suppressed. Further, the thickness of the internal electrode is preferably at least lmm in order to secure mechanical strength.

 Here, it is preferable to provide, on the entire surface or a part of the surface of the internal electrode 9, a secondary electron emission layer 82 having a material power having a larger secondary electron emission coefficient than the electrode material of the internal electrode 9. The thickness of the secondary electron emission layer 82 is preferably lOnm-50 m. Below lOnm, 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 layer in consideration of the occurrence of etching by argon gas. Therefore, the secondary electron-emitting layer may be formed to have a greater thickness, or may be reproduced by performing re-coating. The plasma generated in the plastic container 7 comes into contact with the secondary electron emission layer 82, and secondary electrons are emitted from the secondary electron emission layer 82 into the plasma. At this time, if the secondary electron emission layer 82 is not provided, the secondary electrons are emitted from the surface, but the amount is small. By providing the secondary electron emission layer 82, electrons are easily emitted, and the plasma density is increased. This increases the deposition rate.

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

[0036] Fig. 1 shows a case where only the portion where the internal electrode 9 is inserted into the container is coated, but the entire surface may be coated. A secondary electron emission layer 82 is coated on part of the surface. In the case where the container is inserted, the following can be exemplified in addition to the above-mentioned coating on the container insertion portion.

. The entire surface of the internal electrode 9 may be patterned in a stripe pattern in which lines are arranged. By adjusting the line width and the line interval, the area ratio between the coated surface and the uncoated surface can be optimized, and the plasma density can be increased without preventing ignition of the plasma discharge. In addition, the same area can be adjusted by adjusting the diameter and spacing of the islands, which is good even if the coating is performed in a sea-island shape. It may be coated in a dot shape. Further, a stripe-shaped, sea-island-shaped or dot-shaped coating may be applied to the insertion portion of the container. When a part of the surface is coated with the secondary electron emission layer 82, 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. With the same high-frequency output as the pressure, the film forming speed is increased.

 In FIG. 1, the case where the secondary electron emission layer is provided on both the container insertion portion on the surface of the internal electrode 9 and the entire wall surface of the space 80 of the external electrode 3 is provided on only one of the illustrated forces. May be.

 When the secondary electron emitting layer is made of an alkaline earth metal oxide such as MgO, the secondary electron emitting layer is dried with a nitrogen gas while the film forming chamber 16 is open to the atmosphere. It is preferable to provide drying air blowing means (not shown) for blowing.

 [0040] The container according to the present embodiment includes a container used with a lid, a stopper, or a seal, or a container used in an open state without using them. The size of the opening is determined according to the contents. The plastic container includes a plastic container having an appropriate rigidity and a predetermined thickness, and a plastic container formed of a sheet material having no rigidity. Examples of the filling of 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, including the shape of the container illustrated in FIG. 2, can be employed. The bottom, trunk, shoulder and neck of the container shall be referred to as the shape of the container as shown in Fig. 2. Therefore, these are defined by the height of the container. Absent. Further, the container may be provided with a reduced pressure absorbing surface. When a reduced pressure absorbing surface is provided, it is difficult to completely adhere the inner wall surface of the external electrode and the outer surface of the container over the entire surface. In the CVD film forming apparatus according to the first embodiment, a gap may be provided between the wall surface of the space 80 and the outer surface of the container, so that it is suitable for forming a CVD film on a container having a reduced pressure absorption surface. .

 [0042] The resin used for molding the plastic container of the present embodiment is polyethylene terephthalate resin (PET), polyethylene terephthalate-based copolyester resin (instead of ethylene glycol as the alcohol component of the polyester, a cyclodextrin). Hexandimethanol-based copolymer is called PETG (manufactured by Eastman Chemical), polybutylene terephthalate resin, polyethylene naphthalate, polyethylene S, polypropylene S, polypropylene resin (PP), cycloolefin copolymer Resin (COC, cyclic olefin copolymer), ionomer resin, poly 4-methylpentene 1 resin, polymethyl methacrylate resin, polystyrene resin, ethylene vinyl alcohol copolymer resin, acrylonitrile resin, polychloride Beer fat, poly salty dang biylidene Butter, polyamide resin, polyamideimide resin, polyacetal resin, polycarbonate resin, polysulfone resin, or tetrafluoroethylene resin, Atari mouth-tolyl styrene resin, acrylonitrile butadiene styrene resin. be able to. Among them, PET is particularly preferred.

The container internal gas introducing means 41 introduces a container internal gas supplied from a container internal gas generating source 20 into the plastic container 7. That is, one end 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 gas source 20 inside the vessel via a pipe 22. The gas source 20 inside the container generates a source gas or a discharge gas for plasma.

The source gas is selected as a gas inside the plastic container when forming a CVD film on the inner surface of the plastic container. As a source gas, for example, when a DLC film is formed, aliphatic or aromatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons or the like which are gaseous or liquid at room temperature are used. . In particular, benzene with 6 or more carbon atoms, toluene, 0-xylene, m-xylene, p-xylene, cyclohexane and the like are desirable. When used in containers for food, etc., from the viewpoint of hygiene, aliphatic hydrocarbons, especially ethylene hydrocarbons such as ethylene, propylene or butylene, or acetylene such as acetylene, arylene or 1-butyne. Hydrocarbons are preferred. These raw materials may be used alone or may be used as a mixed gas of two or more kinds. Further, these gases may be used after being diluted with a rare gas such as argon or helium. When forming a silicon-containing DLC film, a Si-containing hydrocarbon-based gas is used.

 [0045] The DLC film referred to in the present embodiment is an i-carbon film or a hydrogenated amorphous carbon film (a

C: H), and includes a hard carbon film. The DLC film is a carbon film of Amorufa focal also has SP ³ bond. A hydrocarbon gas, for example, 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 which can be used for a one-way, rita-navable container such as a carbonated beverage or a sparkling beverage is obtained.

 On the other hand, the discharge gas is selected as the 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 turned into plasma.

[0047] The container external gas introduction means 38 supplies a raw material gas or discharge gas for plasma to an enclosed space (hereinafter referred to as "outside the container" t) outside the plastic container 7 and in the empty space 80. It is to be introduced. 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 inlet (not shown) is provided at a predetermined position of the lid 5 or the external electrode 3 in the film forming chamber 16 through which gas can be introduced outside the container. FIG. 1 shows a case where the lid 5 is provided with a gas inlet outside the container. One side of a pipe 33 is connected starting from the container external gas inlet provided on the lid 5 or the external electrode 3, and the other side of the pipe 33 is connected to a mass flow controller port 35 via a vacuum valve 34. Connected to the side. Piping 3 on the other side of mass flow controller 35 It is connected to an external gas generating source 37 via 6. The container external gas generation source 37 generates a source gas or a discharge gas for plasma.

[0048] Since the container external gas is a raw material gas or a discharge gas to be turned into plasma, it is turned into plasma outside the container, which is a closed space, by the high frequency supplied to the external electrode 3. Since the plasma-formed container external gas is a conductor, high frequency is conducted to the outer surface of the plastic container 7. The high frequency conducted on the wall surface of the plastic container 7 causes a potential difference between the wall surface and the internal electrode 9, and the gas inside the container is turned into plasma inside the plastic container 7.

 [0049] Since the gas inside the container and the gas outside the container are not crossed, plasma is ignited independently of the inside of the container and the outside of the container which is a closed space.

 [0050] The source gas is selected as the container external gas when a CVD film is formed on the outer surface of the plastic container. As the raw material gas, the same kind of gas as that of the raw material gas in 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 kind of gas as that of the discharge gas outside the container is selected.

 [0052] The space 23 in the conductive member 4b is connected to one side of the pipe 13, and the other side of the pipe 13 is connected to a vacuum pump 21 via a vacuum valve 18. This vacuum pump 21 is connected to an exhaust duct 29. The space 23 in the conductive member 4b 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 a vacuum valve 17. .

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

[0054] 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 supply 15 connected to the automatic matching unit 14 via a coaxial cable. The high frequency power supply 15 is grounded.

[0055] The high-frequency power supply 15 generates high-frequency energy, which is an energy for converting the gas outside the container and the gas inside the container into plasma. In order to perform matching quickly and reduce the time required for plasma ignition, it is preferable to use a transistor-type high-frequency power supply and a variable-frequency or high-frequency power supply that performs electronic matching. The frequency of the high frequency power supply is 100kHz-1000MHz. For example, use the frequency of 13.56MHz which is the industrial frequency. For the high frequency output, for example, a 10-2000W output is selected.

 The automatic matching unit 14 adjusts the impedance of the internal electrode 9 and the film formation chamber 16 so as to match the impedance by the inductance C.

 FIG. 5 shows a CVD film forming apparatus according to the second embodiment. The apparatus shown in FIG. 5 is an example in which an external electrode 62 including an upper external electrode 60 and a lower external electrode 61 is used as a film forming chamber. In this case, unlike the above embodiment, no lid is provided. That is, when the external electrode 62 and the internal electrode 9 are in an insulated state, the shape of the film forming chamber 1 can be variously changed. The lower external electrode 61 is supported by elevating means 65, and the external electrode 62 (the film forming chamber 1) can be freely opened and closed by raising and lowering the lower external electrode 61.

 Next, a method of 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 16 is opened to the atmosphere by opening a 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 in a state where the force of the upper external electrode 2 is also removed. An uncoated plastic container 7 is inserted from below the upper external electrode 2 into the space inside the upper external electrode 2 and installed. At this time, the internal electrode 9 is in a state of being 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 by an O-ring 8.

Next, after closing the vacuum valve 17, the vacuum valve 18 is opened, and the vacuum pump 21 is operated. Thereby, the inside of the plastic container 7 is evacuated through the pipe 13 to be a vacuum. At this time, the pressure in the plastic container 7 is 2.6-66 Pa. Simultaneously with this operation, after closing the vacuum valve 31, the vacuum valve 40 is opened and the vacuum pump 25 is operated. This seals The inside of the container, which is a space, is evacuated through a pipe 45 to be a vacuum. The pressure inside the vessel at this time is 2.6-66 Pa.

 Next, the vacuum valve 16 was opened, a gas inside the container was generated in the gas source 20 inside the container, the gas inside the container was introduced into the pipe 22, and the flow rate was controlled by the mass flow controller 19. The gas inside the container is blown out from the gas blowout port 49 through the pipe 11 and the internal electrode 9 at the earth potential. Thereby, the gas inside the container is introduced into the plastic container 7. Then, the pressure inside the plastic container 7 is maintained at a pressure suitable for turning the gas inside the container into plasma, for example, about 6.6 to 665 Pa, and stabilized by a balance between the controlled gas flow rate and the exhaust capacity. Simultaneously with this operation, the vacuum valve 34 is opened, a container external gas is generated in the container external gas generation source 37, 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 gas is blown out of the container outside gas inlet (not shown) through the pipe 33 into the outside of the container, which is a closed space. Thereby, the gas outside the container is introduced into the outside of the container. Then, the inside of the container is kept at a pressure suitable for turning the gas outside the container into plasma, for example, about 6.6 to 665 Pa, by the balance between the controlled gas flow rate and the exhaust capacity, and is stabilized. The flow rates of the gas inside the container and the gas outside the container differ depending on the capacity of the container, and are, for example, 50 to 500 sccm.

Next, a high-frequency output is supplied to the external electrode 3 so that the gas inside the container and the gas outside the container are almost simultaneously turned into plasma to form a DLC film 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 unit 39. The high frequency output is, for example, 10-2000W. As a result, plasma is ignited between the external electrode 3 and the internal electrode 9. At this time, the inside of the plastic container 7 and the outside of the container form a separate space with the wall surface of the plastic container as a boundary, but plasma is ignited in both cases. 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 plasma-contained external gas as a conductor, and the container is also formed inside the plastic container 7. The internal gas is turned into plasma. At this time, the automatic matching unit 14 adjusts the impedance by the inductance and the capacitance C so that the reflected wave from the entire electrode supplying the output becomes the maximum / J. As a result, hydrocarbon-based plasma Is generated, 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 emit secondary electrons by being exposed to plasma, and both the plasma density outside the container and the plasma density inside the container increase. As the plasma density increases outside the container, a high self-bias voltage is applied to the wall of the plastic container. Then, the deposition rate is high and the film is dense. At this time, an increase in the plasma density inside the container contributes to an increase in the deposition rate. When the secondary electron emitting layer is provided (for example, 200 to 500 AZ seconds), the film forming speed is lower than that when the secondary electron emitting layer is not provided (for example, 100 AZ seconds). — 5 times better. The film formation time at this time is as short as about several seconds. Next, the RF output from the high frequency supply means 39 is stopped, the plasma is extinguished, and the formation of the DLC film is completed. At about the same time, the vacuum valves 16 and 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 gas inside the container or the gas outside the container remaining inside the plastic container 7 and inside the container, the vacuum valves 18 and 40 are opened, and these gases are pumped by the vacuum pumps 21 and 25. Exhaust. Thereafter, the vacuum valves 18 and 40 are closed, and the evacuation is terminated. At this time, the pressures inside the plastic container 7 and outside the container are 6.6-665 Pa, respectively. Thereafter, the vacuum valves 17, 31 are opened. As a result, air enters the space 23 inside the lid 5 and the inside of the plastic container 7, and air enters the space inside the container in parallel, and the inside of the film forming chamber 6 is opened to the atmosphere.

 Next, assume that the lower external electrode 1 of the external electrode 3 is detached from the upper external electrode 2.

 The plastic container 7 housed in the space inside the upper external electrode 2 is taken out from below the upper external electrode 2. Alternatively, 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 mode when a raw material gas or a discharge gas is selected as the container external gas or the container internal gas will be described. In the present embodiment, there are three combinations of selection of the gas outside the container and the gas inside the container. This is shown in Table 1.

[table 1] Gas outside the container Gas inside the container CVD film formation After the CVD film formation Outside the container After the process Surface condition Surface condition Gas combination 1 Discharge gas Raw material gas Plasma surface CVD film reforming

 Gas combination 2 Source gas Discharge gas C V D film formation Plasma surface modification

 Gas combination 3 Source gas Source gas C V D film formation C V D film formation

[0065] 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 above-described raw material gas, for example, acetylene gas, is used as the raw material gas, a dense DLC film having gas nori 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 imparts gas barrier properties such as oxygen and carbon dioxide, as well as water vapor barrier properties, and also suppresses adsorption of fragrance components etc. on the container wall and sorption to the container fat can do. On the other hand, the plasma surface modification of the outer surface of the container is as follows. In other words, if a rare gas such as helium or argon, which is an inert gas, is used as a discharge gas for the external gas of the container, the outer surface of the plastic container is roughened by an inert plasma treatment, thereby improving the adhesiveness of a label or the like and improving the ink. Printability and static electricity prevention (dirt adhesion prevention). By using hydrogen, oxygen, nitrogen, water vapor, ammonia gas, carbon tetrafluoride, or a mixed gas thereof as a discharge gas, it is possible to impart functional groups by reactive plasma treatment and improve the adhesion of labels and the like. . Therefore, different functions can be separately provided to the inner surface of the container and the outer surface of the container.

[0066] In 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 above-mentioned source gas, 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 ensured by the DLC film formed on the outer surface of the container. Furthermore, it is possible to realize a reduction in the coefficient of static friction and to prevent external scratches. On the other hand, the plasma surface modification of the inner surface of the container is as follows. That is, microorganisms can be sterilized by using helium, argon, oxygen, nitrogen or the like as the discharge gas of the gas inside the container. This disinfection action is due to only the plasma activated species, and the plasma power is also radiated. Loud. By using nitrogen, oxygen, carbon dioxide, fluorine or a mixed gas thereof as a discharge gas, it is possible to improve the wettability of the inner surface of the container by introducing a polarity by reactive plasma treatment.

 [0067] With gas combination 3, a CVD film can be formed on both the inner surface of the container and the outer surface of the container. When the above-mentioned raw material gas, for example, acetylene gas, is used as the raw material gas, a dense DLC film having gas noria property can be formed on the inner surface and the outer surface of the container. By forming a gas noria DLC film on both walls of a plastic container, a plastic container with an ultra-high gas barrier can be manufactured. In addition, it is possible to reduce the thickness of the DLC film in order to ensure gas barrier properties on both wall surfaces, thereby shortening the film formation time. Furthermore, since the DLC film is formed on the outer surface of the container, it is possible to reduce the coefficient of static friction and to prevent scratches on the outer surface.

 (Embodiment of plasma ignition type device only inside the container)

 FIG. 6 is a conceptual diagram showing the relationship between the basic configuration of the third embodiment of the CVD film forming apparatus according to the present embodiment. The CVD film forming apparatus according to the present embodiment has a space 80 in which the plastic container 7 can be accommodated, the external electrode 3 also serving as a vacuum chamber, and the external electrode 3 insulated from the plastic container 7. An internal electrode 9 that can be inserted and removed, a container internal gas introducing means 41 for introducing a raw material gas to be converted into plasma into the plastic container 7, and a high frequency supply means 39 for supplying high frequency to the external electrode 3. , Is provided. A film forming chamber 16 is composed of the external electrode 3 and the lid 5, and forms a vacuum chamber that can be sealed. Since the CVD film forming apparatus according to the third embodiment is of a type that does not introduce a gas outside the container as a plasma conductor, the wall surface of the space 80 of the external electrode 3 is covered with the plastic container 7 when the plastic container 7 is accommodated. It has a similar shape almost in contact with the outer surface of the stick container 7.

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

[0070] 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 is used to ensure insulation between the internal electrode 9 and the external electrode 3. The lid 5 is formed of an insulating member. The internal electrode 9 is supported by the insulating member 10. In addition, on lid 5 The internal electrode 9 is inserted into the space 80 of the external electrode 3 through the provided space 23 and the mouth opening 52. The tip of the internal electrode 9 is arranged inside the plastic container 7 housed in the space 80.

 The internal electrode 9 has the same configuration as that of the first embodiment, and a material having a larger secondary electron emission coefficient than the electrode material of the internal electrode 9 is provided on the entire surface or a part of the surface of the internal electrode 9. A secondary electron emission layer 82 made of This increases the plasma density in the CVD film forming apparatus according to the second embodiment. This increases the film forming speed. The material, coating mode, and coating method of the secondary electron emission layer 82 are the same as those in the first embodiment. If the secondary electron-emitting layer is made of alkaline earth metal oxide such as MgO, dry air blowing the secondary electron-emitting layer with dry nitrogen gas should be used while the deposition chamber 16 is open to the atmosphere. It is preferable to provide a means (not shown).

 The container internal gas introducing means 41 has the same configuration as in the first embodiment, and the same source gas as in the first embodiment is supplied into the container. The high-frequency supply means 39, the exhaust pipe 13 constituting the exhaust system inside the container, the vacuum pump 21, and the exhaust duct 29 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 raw material gas is supplied only inside the container, and the raw material gas is turned into plasma to form a film. The operation for generating plasma inside the container is the same as that of the CVD film forming apparatus according to the first embodiment. When the secondary electron emitting layer 82 is exposed to 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 AZ seconds), the deposition rate is 2 times lower than when the secondary electron emission layer is not provided (for example, 100 AZ seconds). — 5 times better.

 [0074] In the first to thirteenth embodiments, a PET bottle for beverage is used as a container for forming a thin film inside the container! /, But a container used for other purposes may be used. .

In the first to thirteenth embodiments, a DLC film or a Si-containing DLC film is used as a thin film to be formed by a CVD film forming apparatus. It is also possible to use a film forming apparatus. The DLC film is formed to have a thickness of 0.003 to 5 μm.

Claims

The scope of the claims  [1] A vacuum chamber having a space for accommodating a plastic container and capable of accommodating the plastic container in the space so that gas inside the container and gas outside the container of the plastic container do not cross each other. An external electrode that is also used as the external electrode, an internal electrode that is inserted into and removed from the plastic container in an insulated state from the external electrode, and the container internal gas that is a raw gas or a discharge gas for plasma. A container internal gas introducing means for introducing the inside of the plastic container, a container external gas introducing means for introducing the container external gas, which is a raw material gas for forming a plasma or a discharge gas, into the space, and the external electrode A high frequency supply means for supplying a high frequency to the plastic container, wherein a plastic film is formed on at least one of the inner surface and the outer surface of the plastic container. Be between CVD film-forming apparatus,  A plasma-enhanced CVD method characterized in that a secondary electron-emitting layer having a material power having a higher secondary electron emission coefficient than the electrode material of the external electrode is provided on the entire wall surface or a part of the wall surface of the external electrode. apparatus.  [2] The secondary electron emission layer having a material power having a larger secondary electron emission coefficient than the electrode material of the internal electrode is provided on the entire surface or a part of the surface of the internal electrode. Plasma CVD deposition equipment.  [3] 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 of the plastic container and the gas outside the container do not cross each other. An external electrode that is also used as the external electrode, an internal electrode that is inserted into and removed from the plastic container in an insulated state from the external electrode, and the container internal gas that is a raw gas or a discharge gas for plasma. A container internal gas introducing means for introducing the inside of the plastic container, a container external gas introducing means for introducing the container external gas, which is a raw material gas for forming a plasma or a discharge gas, into the space, and the external electrode A high frequency supply means for supplying a high frequency to the plastic container, wherein a plastic film is formed on at least one of the inner surface and the outer surface of the plastic container. Be between CVD film-forming apparatus, The entire surface or a part of the surface of the internal electrode is more secondary than the electrode material of the internal electrode. A plasma CVD film forming apparatus characterized by providing a secondary electron emitting layer of a material strength with a large electron emission coefficient.  [4] an external electrode having a space capable of accommodating the plastic container and also serving as a vacuum chamber, an internal electrode that is detachably disposed inside the plastic container in an insulated state from the external electrode, A container gas introducing means for introducing a raw material gas for plasma into the plastic container; and a high frequency supply means for supplying a high frequency to the external electrode, wherein a CVD film is formed on an inner surface of the plastic container. In the plasma CVD film forming equipment that forms the film,  A plasma CVD film forming apparatus, wherein a secondary electron emission layer having a material power having a larger secondary electron emission coefficient than the electrode material of the internal electrode is provided on the entire surface or a part of the surface of the internal electrode.  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 an outer wall surface of the external electrode.