JP2003286571A - Apparatus for forming carbon film on inner surface of plastic vessel, and method for manufacturing plastic vessel with carbon-film coated inner surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for coating a carbon film having a superior film quality and a uniform thickness, on the inner surface of a plastic vessel. <P>SOLUTION: This film-forming apparatus is provided with an external electrode having such a size as to surround the periphery of the vessel when the plastic vessel of an article to be treated is inserted therein; an exhaust pipe installed on an end face of the above external electrode in a side where an opening of the above vessel is located, through an insulating member; an internal electrode, which is inserted into the above plastic vessel in the above external electrode from the above exhaust pipe side, and is connected to the ground side; an exhaust means installed to the above exhaust pipe; a gas feeding means for feeding a medium gas to the above internal electrode; and a high-frequency power source connected to the above external electrode; wherein the above internal electrode is provided with a gas spouting part consisting of an insulative material for spouting the medium gas, in a part of the bottom side of the plastic vessel inserted into the above external electrode. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for forming a carbon film on the inner surface of a plastic container and a method for producing an inner carbon film-coated plastic container.

[0002]

2. Description of the Related Art Plastic containers, such as PET bottles, are used for permeation of oxygen from the outside and inside (for example, carbonated drinking water).
On its inner surface to prevent the permeation of carbon dioxide from the
Attempts have been made to coat a carbon film such as LC (Diamond Like Carbon).

As a method of coating a carbon film on the inner surface of such a plastic container, Japanese Patent Laid-Open No. 8-5311 has been proposed.
No. 6 and No. 2788412 (Japanese Unexamined Patent Publication No. Hei 8 (1998)
No. 53,117) discloses a method using high frequency plasma. Japanese Patent Laid-Open No. 9-272567 discloses
As an applied method, a method of coating a carbon film on a film using high frequency plasma is disclosed.
Japanese Patent No. 3072269 (Japanese Patent Laid-Open No. 10-226884) discloses a carbon film coating method corresponding to a special shape container, and Japanese Patent No. 3115252 (Japanese Patent Laid-Open No. 10-258).
No. 825) discloses a method for coating a plurality of containers at the same time as a mass production technology. Further, as a document disclosing a technique of coating a carbon film on a plastic container, “K. Takemoto, et al, Proce.
edings of ADC / FCT '99, p285 '', `` E. Shimamura et al,
10th years IAPRI World Conference 1997, p251 ".

The basic invention of coating a carbon film on a plastic container using high-frequency plasma CVD is described in Japanese Patent No. 2788412 (Japanese Patent Laid-Open No. 8-53116).
No.) will be described with reference to FIG. FIG. 12 is a sectional view of a carbon film coating apparatus for a plastic container using high frequency plasma CVD described in this publication.

The external electrode 201 is installed on a pedestal 202 via a seal plate 203 made of polytetrafluoroethylene, for example. The external electrode 201 has an inner shape that is substantially along the outer shape of the plastic container, for example, the bottle B, to be stored. The external electrode 201 preferably has an inner shape that conforms to the screw shape for the bottle cap, also at the base portion. The external electrode 201 includes a cylindrical main body 201a and a cap portion 201 attached to the upper end of the main body 201a.
b and also serves as a vacuum container. The gas exhaust pipe 204 is connected to the lower portion of the external electrode 201 through the gantry 202 and the seal plate 203.

The internal electrode 205 is inserted in the bottle B housed in the external electrode 201. The internal electrode 205 has a hollow structure, and a plurality of gas blowing holes 206 are formed on the surface thereof. A gas supply pipe 207 for supplying the CVD medium gas penetrates the gantry 202 and the seal plate 203 and communicates with the lower end of the internal electrode 205. The medium gas for CVD is supplied to the supply pipe 2
It is supplied into the internal electrode 205 through 07, and is supplied into the bottle B from the gas blowing hole 206.

The RF input terminal 208 is connected to the lower portion of the external electrode 201 through the frame 202 and the seal plate 203. The RF input terminal 208 is electrically insulated from the gantry 202. In addition, R
The lower end of the F input terminal 208 is connected to the high frequency power supply 210 through the matching unit 209. The external electrode 201
A high frequency power for plasma generation is applied from a high frequency power supply 210 through the matching unit 209 and the RF input terminal 208.

A method of coating a carbon film on the inner surface of a PET bottle using the apparatus having such a configuration will be described.

First, the PET bottle B is inserted into the main body 201a of the external electrode 201, and the cap 201b is attached to the main body 201a to hermetically store the bottle B in the external electrode 201. The gas in the external electrode 201 is exhausted through the gas exhaust pipe 204. At this time, the external electrode 201 is passed through the opening of the seal plate 203.
The gas in the space inside and outside the bottle B stored in is discharged. After reaching the specified vacuum degree (typical value: 10 ⁻² to 10 ⁻⁵ Torr), the medium gas is supplied to the internal electrode 205 through the gas supply pipe 207 at a flow rate of, for example, 10 to 50 mL / min. The gas is blown into the bottle B through the gas blowing hole 206 of No. As the medium gas, for example, aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, aromatic hydrocarbons, oxygen-containing hydrocarbons and nitrogen-containing hydrocarbons are used. The pressure in the bottle B is set to, for example, 2 × 10 ⁻¹ to 1 × 10 ⁻² Torr depending on the balance between the gas supply amount and the exhaust amount.
After that, a high frequency power of 50 to 1000 W is applied from the high frequency power supply 210 to the external electrode 101 through the matching unit 209 and the RF input terminal 208.

By applying such high frequency power to the external electrode 201, the external electrode 201 and the internal electrode 205 are
Plasma is generated during the period. At this time, plastic bottle B
Is stored in the external electrode 201 with almost no space therebetween, so that plasma is generated in the plastic bottle B. The medium gas is dissociated by the plasma or further ionized to generate a film-forming species for forming a carbon film, and the film-forming species is deposited on the inner surface of the bottle B to form a carbon film. After forming the carbon film to a predetermined thickness, stop applying high frequency power, stop supplying medium gas, exhaust residual gas,
Nitrogen, a rare gas, air, or the like is supplied into the external electrode 201 to return the pressure in this space to atmospheric pressure. After this, the bottle B
Is removed from the external electrode 201. In this method, it takes 2-3 seconds to form a carbon film having a thickness of 30 nm.

[0011]

However, the invention of Japanese Patent No. 2788412 described above has the following problems.

The medium gas is supplied into a plastic container (for example, bottle B) from a plurality of gas outlets 206 opened along the axial direction of the internal electrode 205 and exhausted from the mouth of the plastic container. Therefore, the gas flow path in the plastic container is a space sandwiched between the internal electrode and the external electrode, and the space near the mouth of the plastic container has a large conductance, which promotes the gas flow from the gas outlet holes. The gas flow from the gas outlet near the bottom of the container far from the mouth is stopped. As a result, the medium gas near the bottom of the container is exposed to plasma for a longer period of time than the gas near the mouth of the container, and the molecules bound by the gas phase reaction may become too large and become powdery. is there.

Further, the gas flow rate, pressure, and
Depending on the conditions such as the electric field distribution, locally concentrated discharge may occur inside or near the gas outlet, and this discharge concentration may cause generation of powder, uneven film thickness, loss of high frequency power, electrode There is a problem such as temperature rise. In particular, the powdery substance does not coat the surface of the container as a thin film, but becomes a foreign substance deposited on it. The generation of such foreign matter is inconvenient in the following points.

A). Even if a large number of powdery substances are deposited, there is a gap between them, so that the gas barrier effect unlike when using a carbon film does not occur.

B). Powdery substances that may be mixed in the beverage remain in the container.

C). The generated powder flows into the exhaust means and causes failure of the exhaust means.

It is an object of the present invention to provide a carbon film forming apparatus on the inner surface of a plastic container capable of preventing local discharge generated at a gas outlet and preventing powder from being generated thereby. .

An object of the present invention is to provide an apparatus for forming a carbon film on the inner surface of a plastic container, which has a good film quality on the inner surface of the plastic container and which can be coated with a carbon film having a uniform thickness.

It is an object of the present invention to provide a method of manufacturing a plastic container having a good film quality and a carbon film having a uniform film thickness coated on the inner surface.

An object of the present invention is to provide an apparatus for forming a carbon film on the inner surface of a plastic container, which has a good film quality on the inner surface of the plastic container and can coat a carbon film having a uniform thickness at a high speed. To do.

An object of the present invention is to provide a method for producing a plastic container having a good film quality and a carbon film having a uniform film thickness coated on the inner surface at a high speed.

[0022]

The apparatus for forming a carbon film on the inner surface of a plastic container and the method for manufacturing an inner surface carbon film-coated plastic container according to the present invention are characterized by having the following configurations.

1) An external electrode having a size that surrounds the outer circumference of a plastic container, which is an object to be processed, and an insulating member on the end surface of the external electrode on the side where the mouth of the container is located. An exhaust pipe attached via
An internal electrode inserted into the plastic container in the external electrode from the exhaust pipe side and connected to the ground side, an exhaust means attached to the exhaust pipe, and a medium gas for supplying the internal electrode with medium gas An insulating material for supplying a medium gas to a portion of the internal electrode, which is located on the bottom side of a plastic container inserted into the external electrode, comprising: a gas supply unit; and a high-frequency power source connected to the external electrode. An apparatus for forming a carbon film on the inner surface of a plastic container, characterized in that a gas blowing section made of is provided.

2) In producing an inner carbon film-coated plastic container using the carbon film forming apparatus of 1) above,
(A) a step of inserting a plastic container, which is an object to be processed, into an external electrode; and (b) an internal electrode provided with a gas blowing part made of an insulating material, which is provided on the side where the mouth part of the container is located. A step of inserting the gas blower into the inside of the plastic container from an exhaust pipe attached to the end surface of the external electrode via an insulating member so that the gas blowing part is located on the bottom side of the container; and (c) gas inside and outside the container. After being exhausted through the exhaust pipe by the exhaust pipe means, the medium gas is supplied to the internal electrode by the gas supply means, and the medium gas is blown into the plastic container from the gas blowing portion of the internal electrode to blow the inside of the plastic container. A step of setting a predetermined gas pressure in the exhaust pipe containing the same; and Surrounding parts electrodes to generate plasma, the inner surface carbon film manufacturing method of the coated plastic containers, which comprises a step of coating a carbon film on the plastic container inner surface by dissociating the medium gas by the plasma.

3) An external electrode having a size that surrounds the plastic container, which is the object to be processed, when the container is inserted, and an insulating member on the end surface of the external electrode on the side where the mouth of the container is located. An attached exhaust pipe, an internal electrode inserted from the exhaust pipe side into the plastic container inside the external electrode and connected to the ground side, an exhaust means attached to the exhaust pipe, and the internal electrode. A gas supply unit for supplying a medium gas; a high-frequency power supply connected to the internal electrode; and a bias power supply connected to the external electrode, wherein the internal electrode is inserted into the external electrode. Charcoal to the inner surface of the plastic container, characterized in that a gas blowing part made of an insulating material for blowing the medium gas is provided in the part located on the bottom side of the plastic container. Film forming apparatus.

4) When manufacturing an inner carbon film-coated plastic container using the carbon film forming apparatus of 3) above,
(A) a step of inserting a plastic container, which is an object to be processed, into an external electrode; and (b) an internal electrode provided with a gas blowing part made of an insulating material, which is provided on the side where the mouth part of the container is located. A step of inserting the gas blower into the inside of the plastic container from an exhaust pipe attached to the end surface of the external electrode via an insulating member so that the gas blowing part is located on the bottom side of the container; and (c) gas inside and outside the container. After being exhausted through the exhaust pipe by the exhaust pipe means, the medium gas is supplied to the internal electrode by the gas supply means, and the medium gas is blown into the plastic container from the gas blowing portion of the internal electrode to blow the inside of the plastic container. A step of setting a predetermined gas pressure in the exhaust pipe including the step of: (d) applying a high frequency power from the bias power supply to the external electrode, and Supplying wave power to the internal electrode through the gas supply pipe to generate plasma in the plastic container, and the plasma dissociates the medium gas to coat a carbon film on the inner surface of the plastic container. A method for producing an inner carbon film-coated plastic container, comprising:

5) An external electrode having a size that surrounds the container to be processed when the plastic container to be processed is inserted, and at least a mouth and a shoulder of the container when the plastic container to be processed is inserted. A spacer made of a dielectric material interposed between the external electrode and the external electrode, an exhaust pipe attached to the end surface of the external electrode on the side where the mouth portion of the container is located via an insulating member, and inside the external electrode Is inserted from the exhaust pipe side into the plastic container of
An internal electrode connected to the ground side, an exhaust unit attached to the exhaust pipe, a gas supply unit for supplying a medium gas to the internal electrode, and a high-frequency power source connected to the external electrode. The inner electrode is provided with a gas blowing portion made of an insulating material for blowing a medium gas in a portion located on the bottom side of the plastic container inserted into the outer electrode. Carbon film forming equipment

6) When manufacturing an inner carbon film-coated plastic container using the carbon film forming apparatus of 5) above,
(A) A plastic container, which is an object to be processed, is enclosed in an external electrode and a spacer made of a dielectric material, at least the outer periphery of the mouth and shoulder of the container is surrounded by the spacer. A step of inserting the outer electrode so as to be surrounded by the outer electrode; and (b) an inner electrode provided with a gas blowing portion made of an insulating material, on an end surface of the outer electrode on the side where the mouth portion of the container is located. A step of inserting the gas blower into the inside of the plastic container from an exhaust pipe attached via an insulating member so that the gas blowing part is located on the bottom side of the container; After exhausting through the exhaust pipe, a medium gas is supplied to the internal electrode by a gas supply means, and the medium gas is blown into the plastic container from a gas outlet of the internal electrode. A step of setting a predetermined gas pressure in the exhaust pipe including the inside of the plastic container, and (d) supplying high frequency power from a high frequency power source to the external electrode to generate plasma around the internal electrode located in the plastic container. And a step of dissociating the medium gas by the plasma to coat the carbon film on the inner surface of the plastic container.

7) An external electrode having a size that surrounds the container to be processed when the plastic container to be processed is inserted, and at least the mouth and shoulder of the container when the plastic container to be processed is inserted. A spacer made of a dielectric material interposed between the external electrode and the external electrode, an exhaust pipe attached to the end surface of the external electrode on the side where the mouth of the container is located via an insulating member, and the inside of the external electrode An internal electrode inserted into the plastic container, a gas supply pipe having one end connected to the internal electrode and the other end extending to the exhaust pipe side and also serving as a power supply terminal, at least in the external electrode and An earth shield pipe, which is arranged on the outer periphery of the gas supply pipe portion located inside the exhaust pipe near the mouth of the container, is grounded, exhaust means attached to the exhaust pipe, A gas supply means for supplying a medium gas to the gas supply pipe, a high-frequency power supply connected to the gas supply pipe, and a bias power supply connected to the external electrode, wherein the internal electrode is A device for forming a carbon film on the inner surface of a plastic container, wherein a gas blowing portion made of an insulating material for blowing a medium gas is provided in a portion located on the bottom side of the plastic container inserted into the external electrode.

8) In manufacturing an inner carbon film-coated plastic container using the carbon film forming apparatus of 7) above,
(A) A plastic container, which is an object to be processed, is enclosed in an external electrode and a spacer made of a dielectric material, at least the outer periphery of the mouth and shoulder of the container is surrounded by the spacer. A step of inserting the outer electrode so that the outer periphery is surrounded by the outer electrode; and (b) a gas supply pipe having a grounded earth shield pipe arranged on the outer periphery is connected,
An internal electrode provided with a gas blowout part made of an insulating material, the gas inside the plastic container from an exhaust pipe attached to the end surface of the external electrode on the side where the mouth part of the container is located via an insulating member. And (c) exhausting gas inside and outside the container through the exhaust pipe by exhaust pipe means, and then supplying medium gas from the gas supply pipe means to the inside of the container. Supplying gas to the electrode through the gas supply pipe, and blowing a medium gas into the plastic container from the gas blowing portion of the internal electrode to set a predetermined gas pressure in the exhaust pipe including the inside of the plastic container; A high frequency power is applied to the external electrode from a bias power source, and a high frequency power is supplied from the high frequency power source to the internal electrode through the gas supply pipe. A plasma is generated in the plastic container, and the medium gas is dissociated by the plasma to coat the carbon film on the inner surface of the plastic container. .

9) An external electrode having a size that surrounds the container to be processed when the container is inserted, and an insulating member on the end surface of the external electrode on the side where the mouth of the container is located. An attached exhaust pipe, an internal electrode inserted into the plastic container in the external electrode from the exhaust pipe side and provided with a gas blowing portion for blowing out a medium gas, and one end thereof is connected to the internal electrode. , A gas supply pipe having the other end extended to the exhaust pipe side and also serving as a power supply terminal, and a tip at the outer periphery of the gas supply pipe portion located at least in the external electrode and in the exhaust pipe near the mouth of the container Is provided with a desired gap from the internal electrode and is grounded, and the gas supply is located in a gap region between the internal electrode and the tip of the internal shield tube. An insulating tube at least covered with, an exhaust means attached to the exhaust pipe, a gas supply means for supplying a medium gas to the gas supply pipe, a high-frequency power supply connected to the gas supply pipe, An apparatus for forming a carbon film on an inner surface of a plastic container, comprising: a bias power source connected to the external electrode.

10) In producing an inner carbon film-covered plastic container using the carbon film forming apparatus of 9) above,
(A) A step of inserting a plastic container, which is an object to be processed, into an external electrode, and (b) a gas supply pipe having an insulating tube and a grounded earth shield pipe arranged on the outer periphery in this order is connected, and a gas is blown out. Inserting an internal electrode provided with a portion into the inside of the plastic container from an exhaust pipe attached to the end surface of the external electrode on the side where the mouth of the container is located via an insulating member, (c) After the gas inside and outside the container is exhausted through the exhaust pipe by the exhaust pipe means, the medium gas is supplied from the gas supply pipe means to the internal electrode, and the medium gas is supplied into the plastic container from the gas blowing portion of the internal electrode. Blowing out to set a predetermined gas pressure inside the exhaust pipe including the inside of the plastic container; and (d) applying high frequency power from the bias power supply to the external electrode. In both cases, high-frequency power is supplied from the high-frequency power source to the internal electrode through the gas supply pipe, plasma is generated in the plastic container, and the medium gas is dissociated by the plasma to form a carbon film on the inner surface of the plastic container. And a step of coating the inner surface carbon film-coated plastic container.

11) An external electrode having a size that surrounds the container to be processed when the plastic container to be processed is inserted, and at least a mouth and a shoulder of the container when the plastic container to be processed is inserted. A spacer made of a dielectric material interposed between the external electrode and the external electrode, an exhaust pipe attached to the end surface of the external electrode on the side where the mouth of the container is located via an insulating member, and the inside of the external electrode An internal electrode inserted into the plastic container from the exhaust pipe side and provided with a gas blowing portion for blowing out a medium gas; one end is connected to the internal electrode and the other end extends to the exhaust pipe side. Gas supply pipe also serving as a power supply terminal, and a tip inside the outer periphery of the gas supply pipe portion located at least in the external electrode and in the exhaust pipe near the mouth of the container. Are spaced a desired gap To pole, a ground shield tube which is grounded, and at least the coated insulated tube to the gas supply pipe located in the gap region between the tip of the inner electrode and the earth shield tube,
Exhaust means attached to the exhaust pipe, gas supply means for supplying a medium gas to the gas supply pipe, a high-frequency power supply connected to the gas supply pipe, and a bias connected to the external electrode An apparatus for forming a carbon film on the inner surface of a plastic container, which is equipped with a power supply.

12) In manufacturing an inner carbon film-coated plastic container using the carbon film forming apparatus of 11), (a) place the plastic container, which is the object to be treated, in the outer electrode and in the spacer made of a dielectric material. In such a manner that at least the outer periphery of the mouth and shoulder of the container is surrounded by the spacer and the outer periphery of the other container part is surrounded by the external electrode, and (b) an insulating tube and a ground. A gas supply pipe having a grounded earth shield pipe arranged in this order on the outer periphery is connected, and an inner electrode provided with a gas blowing portion is provided with an insulating member on the end surface of the external electrode on the side where the mouth portion of the container is located. Inserting into the interior of the plastic container from an exhaust pipe attached via
(C) After the gas inside and outside the container is exhausted through the exhaust pipe by the exhaust pipe means, the medium gas is supplied from the gas supply pipe means to the internal electrode, and the gas blowing part of the internal electrode into the plastic container. A step of blowing out a medium gas to set a predetermined gas pressure inside the exhaust pipe including the inside of the plastic container, and (d) applying high frequency power from a bias power supply to the external electrode and applying high frequency power from a high frequency power supply. Supplying the internal electrode through the gas supply pipe to generate plasma in the plastic container, and dissociating the medium gas by the plasma to coat a carbon film on the inner surface of the plastic container. A method of manufacturing a plastic container coated with an inner carbon film.

[0035]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below with reference to the drawings.

(First Embodiment) FIG. 1 is a sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to the first embodiment, and FIG. 2 is an enlarged sectional view showing an internal electrode of FIG.

A cylindrical support member 2 having flanges 1a and 1b at the upper and lower ends is placed on an annular base 3. The cylindrical external electrode body 4 made of metal is arranged in the support member 2. Disk-shaped metal external electrode bottom member 5
Is detachably attached to the bottom of the external electrode 4. The external electrode body 4 and the external electrode bottom member 5
Thus, a bottomed cylindrical external electrode 6 having a space of a size in which a plastic container (for example, a plastic bottle) B for forming a carbon film can be installed is configured. Disc-shaped insulator 7
Are arranged between the base 3 and the external electrode bottom member 5.

The external electrode bottom member 5, the disk-shaped insulator 7 and the base 3 are integrally moved up and down with respect to the external electrode body 4 by a pusher (not shown), and the external electrode body 4 Open and close the bottom.

The annular insulating member 8 is placed on the upper surface of the external electrode 6 such that the upper surface of the annular insulating member 8 is flush with the upper flange 1a of the tubular supporting member 2. The gas exhaust pipe 10 having the upper and lower flanges 9a and 9b includes the upper flange 1a of the support member 2 and the annular insulating member 8.
Is placed on the upper surface of. The exhaust pipe 10 is grounded. The gas exhaust pipe 10 is fixed to the support member 2 by screwing a screw (not shown) from the lower flange 9b of the exhaust pipe 10 to the upper flange 1a of the support member 2. Further, a screw (not shown) is attached to the exhaust pipe 10.
The exhaust pipe 10 by threading the annular insulating portion 8 from the lower flange 9b of the
Is fixed to the annular insulating member 8 and the external electrode 6, and the annular insulating member 8 is also fixed to the external electrode 6. The exhaust pipe 10 is fixed to the annular insulating member 8 and the external electrode 6 only when the exhaust pipe 1 is fixed.
0 and the external electrode 6 have a mounting structure such that they are not electrically connected by a screw. The branch gas exhaust pipe 11 is connected to the side wall of the gas exhaust pipe 10, and an exhaust facility such as a vacuum pump (not shown) is attached to the other end thereof. The lid 12 is attached to the upper flange 9 a of the exhaust pipe 10.

For example, a high frequency power source 13 that outputs high frequency power having a frequency of 13.56 MHz is connected to the main body 4 of the external electrode 6 through a cable 14 and a power supply terminal 15. The matching device 16 is interposed in the cable 15 between the high frequency power supply 13 and the power supply terminal 15.

The gas supply pipe 17 penetrates the lid 12 and is inserted through the gas exhaust pipe 10 into the body 4 of the external electrode 6 at a position corresponding to the mouth of the plastic bottle B. The substantially cylindrical internal electrode 18 made of metal is arranged near the bottom of the PET bottle B inserted into the external electrode 6, and its upper end is detachably attached to the lower end of the gas supply pipe 18. . As shown in FIGS. 1 and 2, the internal electrode 18 has a gas flow path 19 cut out in the central axis thereof, and is a gas blowout portion made of an insulating material for blowing out a medium gas at the bottom portion, for example, plastic or ceramic. A gas blowing pipe 20 made of an insulating material such as the above is inserted.

The diameter of the internal electrode 18 is not more than the diameter of the mouthpiece of the bottle B.

The internal electrodes 18 are made of a heat-resistant metal material such as tungsten or stainless steel, but may be made of aluminum. If the surface of the internal electrode 18 is smooth, the carbon film deposited on the surface of the internal electrode 18 may be easily peeled off. Therefore, the surface of the internal electrode 18 is previously sandblasted,
It is preferable to increase the surface roughness to make it difficult for the carbon film deposited on the surface to peel off. However, also in the method of smoothing the surface described above, if the carbon film to be deposited is easily peeled off by making it extremely smooth and it is prevented from remaining on the internal electrodes,
Another advantage is that the internal electrode cleaning is not required.

Next, a method for manufacturing an inner carbon film-covered plastic container using the carbon film forming apparatus shown in FIG. 1 will be described.

The external electrode bottom member 5, the disk-shaped insulator 7 and the base 3 are removed by a pusher (not shown) to open the bottom of the external electrode body 4. Then, after inserting the plastic container, for example, the PET bottle B, from the bottom side of the opened external electrode body 4 from the mouth side of the bottle B, the external electrode bottom member 5 is attached to the bottom side of the external electrode body 4 by a pusher (not shown). By attaching the disk-shaped insulator 7 and the base 3 in this order, the PET bottle B is placed in the internal space of the external electrode 6 including the external electrode body 4 and the external electrode bottom member 5 as shown in FIG. Store. At this time, the plastic bottle B is communicated with the exhaust pipe 10 through its mouth.

Next, the gas inside and outside the exhaust pipe 19 and the plastic bottle B is exhausted through the branch exhaust pipe 20 and the exhaust pipe 19 by an exhaust means (not shown). Subsequently, the medium gas is supplied to the gas flow path 19 of the internal electrode 18 through the gas supply pipe 17, and is blown out into the plastic bottle B from the gas blowing pipe 20 made of an insulating material and attached to the bottom of the internal electrode 18. This medium gas further flows toward the mouth of the plastic bottle B. Then, the gas supply amount and the gas exhaust amount are balanced and the inside of the plastic bottle B is set to a predetermined gas pressure.

Next, high frequency power having a frequency of 13.56 MHz is supplied from the high frequency power supply 13 to the main body 4 of the external electrode 6 through the cable 14, the matching box 16 and the power supply terminal 15. At this time, plasma is generated around the internal electrodes 18. By the generation of such plasma, the medium gas is dissociated by the plasma, and the inner surface of the PET bottle B in the external electrode 6 is coated with a uniform carbon film having a uniform thickness.

After the thickness of the carbon film reaches a predetermined thickness, the supply of high frequency power from the high frequency power supply 13 is stopped, the supply of medium gas is stopped, the residual gas is exhausted, and the gas is exhausted. After stopping, nitrogen, noble gas, air, or the like is supplied into the PET bottle B through the gas supply pipe 17 and the gas flow path 19 of the internal electrode 18 and the gas blowing pipe 20, and the inside and outside of the PET bottle B are brought to atmospheric pressure. Return and take out the inner carbon film-coated PET bottle. After that, the plastic bottle B is replaced according to the above-described order, and the next PET bottle coating operation is started.

The medium gas is basically hydrocarbon, for example, alkanes such as methane, ethane, propane, butane, pentane and hexane; ethylene, propylene,
Alkenes such as butene, pentene and butadiene; alkynes such as acetylene; benzene, toluene, xylene,
Aromatic hydrocarbons such as indene, naphthalene and phenanthrene; cycloparaffins such as cyclopropane and cyclohexane; cycloolefins such as cyclopentene and cyclohexene; oxygen-containing hydrocarbons such as methyl alcohol and ethyl alcohol; methylamine, ethylamine,
Nitrogen-containing hydrocarbons such as aniline can be used, and carbon monoxide, carbon dioxide, etc. can also be used. In addition, for stabilizing plasma and optimizing plasma characteristics, Ar, H
A rare gas such as e may be mixed with the medium gas.

The high frequency power is generally 13.56M.
However, the frequency is not limited to this. Further, the application of these electric powers may be continuous or intermittent (pulse-like).

As described above, according to the first embodiment, by supplying the medium gas into the plastic bottle B from the bottom of the internal electrode 18, the flow of gas from the bottom of the plastic bottle B toward the mouth is forcibly generated. be able to. Therefore, it is possible to prevent a gas retention portion from being formed in the plastic bottle B. As a result, the inner surface of the PET bottle B can be coated with a carbon film having a uniform film thickness with good film quality with less contamination.

Further, the medium gas is blown out from the gas blowing pipe 20 made of an insulating material inserted in the bottom of the internal electrode 18 to prevent the plasma from being locally concentrated inside or near the gas blowing hole. You can

That is, although providing the gas blowing portion at the bottom of the internal electrode can achieve the above-mentioned effects, on the other hand, depending on the plasma generation conditions such as the supply amount of the medium gas and the pressure in the plastic bottle B, the inside of the metal is made. When the gas blowing hole is directly opened at the bottom of the electrode as a gas blowing portion, plasma may be locally generated inside or near the gas blowing hole. When the plasma is locally generated in the vicinity of the gas blowout hole at the bottom of the internal electrode in this way, the plasma density at that location becomes high, and a large amount of powder is generated,
Contamination (powder) may be mixed in the inner surface of the PET bottle B, or the film thickness may become uneven.

From the above, as shown in FIG. 2, the gas blowing pipe 2 made of an insulating material is provided at the bottom of the internal electrode 18.
By inserting 0 and blowing out the medium gas from the gas blowing pipe 20, local concentration of plasma in the vicinity of the gas blowing pipe 20 is prevented and the density of the plasma generated in the plastic bottle B is made uniform. it can. As a result, the inner surface of the PET bottle B can be coated with a carbon film having a good film quality with less powder mixture and a uniform film thickness.

Therefore, according to the first embodiment, an inner carbon film-coated PET bottle having an excellent barrier property which prevents permeation of oxygen from the outside and permeation of carbon dioxide from the inside (for example, carbonated drinking water) is manufactured. be able to.

(Example 1) As the internal electrode 18, a gas blow-out tube 20 made of polytetrafluoroethylene and having an inner diameter of 1 mm was inserted into the bottom of a stainless piece-sealed tube having an outer diameter of 16 mm and a length of 70 mm shown in FIGS. The one with the worn structure was used.

This internal electrode 18 is replaced with the external electrode 6 shown in FIG.
Insert it in the plastic bottle B stored inside and use C as the medium.
₂ H ₂ gas, the gas flow rate is 20 sccm, the gas pressure in the PET bottle B and the exhaust pipe 10 is 0.1 Torr, and the high frequency supplied from the high frequency power source is a carbon film on the inner surface of the PET bottle B under the conditions of 13.56 MHz. Was coated.

(Comparative Example 1) The outer diameter of the inner electrode was 16 m.
m, a carbon film was formed on the inner surface of the PET bottle B by the same method as in Example 1 except that one having a structure in which a single gas blowout hole having a hole diameter of 1 mm was bored in the bottom of a stainless piece sealed tube having a length of 70 mm was used. Coated.

As a result, in Example 1, the inner surface of the PET bottle B could be coated with the carbon film. In contrast, in Comparative Example 1, a black powder film was formed on the inner surface of the bottom of the PET bottle B, and a large amount of powder was generated. It is considered that the formation of this black powder film is caused by the locally generated high-density plasma inside and in the vicinity of the gas blowing hole.

In the first embodiment, the gas blowing part made of the insulating material is constituted by the gas blowing pipe 20 made of the insulating material shown in FIG. 2. However, the present invention is not limited to this. For example, as shown in FIG. The gas blow-out portion made of is composed of a cap 22 made of an insulating material such as plastic or ceramic with a gas blow-out hole 21 opened in the direction of the central axis. You may attach to the bottom part of the electrode 18 so that it may connect with the said gas flow path 19. In such a configuration shown in FIG. 3, a gas blowing hole may be opened in the side wall of the cap 22.

(Second Embodiment) FIG. 4 is a sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to the second embodiment. In FIG. 4, the same members as those in FIG. 1 referred to in the first embodiment described above are designated by the same reference numerals and the description thereof will be omitted.

This carbon film forming apparatus comprises a bias power source 2
3 is connected to the external electrode body 4 of the external electrode 6 through the cable 24 and the power supply terminal 25. The matching device 26 is
The cable 24 is interposed between the bias power source 23 and the power supply terminal 25.

The lid 12, which has an insulating ring 26 at the center and is grounded, is airtightly fixed to the upper flange 9a of the gas exhaust pipe 10. The housing 27 is attached on the lid 12.

The gas supply pipe 17 to which the internal electrode 18 is detachably attached at the lower end also serves as a terminal for high-frequency power, penetrates the insulating ring 26 of the lid 12 from the inside of the housing 27, and is connected to the gas exhaust pipe. It is inserted into the main body 4 of the external electrode 6 (in the portion corresponding to the central portion of the plastic bottle B to be inserted) through 10. The upper end of the gas supply pipe 17 is connected to the lower end of a gas introduction pipe 28 that is inserted from the outside through the housing 27 via an insulating joint 29. As shown in FIGS. 4 and 5, the internal electrode 18 has a gas flow path 19 cut out in its central axis and a gas blow-out portion made of an insulating material for blowing out a medium gas at the bottom, such as plastic, A gas blowing pipe 20 made of an insulating material such as ceramic is inserted.

Flange tube 30 and this flange tube 30
The earth shield pipe 31 connected to the lower end covers the gas exhaust pipe 10 and the portion of the gas supply pipe 17 located inside the body 4 of the external electrode 6 corresponding to the center of the plastic bottle B. It is arranged. In addition,
The earth shield pipe 31 is located from the gas exhaust pipe 10 near the mouth of the plastic bottle B to a portion corresponding to the center of the plastic bottle B. The upper end of the flange tube 30 is connected to the back surface of the lid 12. That is, the earth shield pipe 31 is connected to the grounded lid 12 through the flange pipe 30.

The high-frequency power source 32 is connected to the side surface of the gas supply pipe 17 which also functions as a terminal for high-frequency power, through a cable 33 and a power supply terminal 34. Matching device 35
Is interposed in the cable 33 between the high frequency power supply 32 and the power supply terminal 34.

Next, a method for manufacturing an inner carbon film-covered plastic container using the carbon film forming apparatus shown in FIG. 4 will be described.

The external electrode bottom member 5, the disk-shaped insulator 7 and the base 3 are removed by a pusher (not shown) to open the bottom of the external electrode body 4. Then, after inserting the plastic container, for example, the PET bottle B, from the bottom side of the opened external electrode body 4 from the mouth side of the bottle B, the external electrode bottom member 5 is attached to the bottom side of the external electrode body 4 by a pusher (not shown). By attaching the disk-shaped insulator 7 and the base 3 in this order, the PET bottle B is placed in the internal space of the external electrode 6 including the external electrode body 4 and the external electrode bottom member 5 as shown in FIG. Store. At this time, the plastic bottle B is communicated with the exhaust pipe 10 through its mouth.

Next, the gas inside and outside the exhaust pipe 10 and the plastic bottle B is exhausted through the branch exhaust pipe 11 and the exhaust pipe 10 by an exhaust means (not shown). Subsequently, the medium gas is supplied to the gas flow path 19 of the internal electrode 18 through the gas introduction pipe 28 and the gas supply pipe 17, and the plastic bottle B is supplied from the gas blowing pipe 20 made of an insulating material and attached to the bottom of the internal electrode 18. Let it blow out. This medium gas further flows toward the mouth of the plastic bottle B. Then, the gas supply amount and the gas exhaust amount are balanced and the inside of the plastic bottle B is set to a predetermined gas pressure.

Next, bias power is supplied from the bias power source 23 to the external electrode 6 through the cable 24, the matching box 26 and the power supply terminal 25. Thereafter or at the same time, high-frequency power is supplied from the high-frequency power supply 32 to the gas supply pipe 17 through the cable 33, the matching device 35 and the power supply terminal 34, and the high-frequency power is supplied to the internal electrode 18 through the gas supply pipe 17. . At this time, plasma is generated around the internal electrodes 18. Further, since the exhaust pipe 10 located above the external electrode 6 is grounded, the exhaust pipe 10 is used as a reference potential for the external electrode 6.
Can apply a bias voltage to the internal electrode 18, that is, to the generated plasma.

As a result, a) When high high frequency power is used,
In particular, a high electron density can be obtained under low gas pressure conditions as compared with high frequency power, so the frequency of collisions with the medium gas increases and the density of film forming species can be increased. B) Adjusting the bias power changes the potential difference from the plasma potential. Therefore, the ion energy incident on the inner surface of the plastic bottle B can be adjusted,
c) Since the ion density is proportional to the electron density, the ion flux incident on the inner surface of the plastic bottle B can be controlled by using it together with the adjustment of the potential difference. Bias power was applied to the film formation species obtained when the medium gas was dissociated by the plasma by the generation of the plasma and the drawing of the plasma to the external electrode 6 by applying the bias voltage to the internal electrode 18. A uniform and high-quality carbon film having a uniform thickness can be coated on the inner surface of the PET bottle B in the external electrode 6 at a high speed.

After the thickness of the carbon film reaches a predetermined value, the bias power supply and the high-frequency power supply 32 from the bias power supply 23 and the high-frequency power supply 32 are stopped, the supply of the medium gas is stopped, and the residual gas remains. After exhausting the gas and stopping the exhaust of the gas, nitrogen, rare gas, air or the like is introduced into the gas introducing pipe 2
8 through the gas supply pipe 17 through the gas flow path 19 of the internal electrode 18 and the gas blowing pipe 20
The inside of the plastic bottle B is returned to atmospheric pressure,
Take out the plastic bottle coated with the inner carbon film. After that, the plastic bottle B is replaced according to the above-described order, and the next PET bottle coating operation is started.

As the medium gas, the same gas as described in the first embodiment can be used.

The high high frequency power is generally 30 to 30.
It is defined as 0 MHz, but is not limited to this. Further, the application of these electric powers may be continuous or intermittent (pulse-like).

The bias power is generally 13.56.
Although the frequency band of 100 MHz to 1000 W is used, the frequency is not limited to this. Further, the application of the bias power may be continuous or intermittent (pulse-like).

As described above, according to the second embodiment, by supplying the medium gas into the plastic bottle B from the bottom of the internal electrode 18, the gas flow from the bottom of the plastic bottle B toward the mouth is forcibly generated. It can be done. Therefore, it is possible to prevent a gas retention portion from being formed in the plastic bottle B. As a result, the inner surface of the PET bottle B can be coated with a carbon film having a uniform film thickness with good film quality with less contamination.

Further, the medium gas is blown out from the gas blowing pipe 20 made of an insulating material inserted in the bottom portion of the internal electrode 18, so that the discharge is concentrated near the gas blowing pipe 20 as in the first embodiment. The density of the plasma generated in the PET bottle B can be made uniform by preventing it. As a result, the inner surface of the PET bottle B can be coated with a carbon film having a good film quality with less powder mixture and a uniform film thickness.

Further, by generating plasma and drawing a bias voltage to the internal electrode 18 to draw the plasma to the external electrode 6, bias power is applied to the film forming species obtained when the medium gas is dissociated by the plasma. The inner surface of the plastic bottle B in the external electrode 6 thus formed can be coated with a uniform and uniform carbon film of high quality at a high speed.

Therefore, it is possible to mass-produce an inner carbon film-coated PET bottle having an excellent barrier property which prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water).

Further, between the gas supply pipe 17 to which high-frequency power is applied and the grounded exhaust pipe 10 (that is, the exhaust pipe 1).
Similarly, in (0), unnecessary plasma is generated and the coating efficiency of the carbon film is reduced. For this reason, the earth shield pipe 31 is arranged on the outer circumference of the gas supply pipe 17 so as to be positioned inside the gas exhaust pipe 10 near the mouth of the plastic bottle B, and the flange for supporting the earth shield pipe 31. By grounding through the pipe 30, even if high-frequency power is supplied to the gas supply pipe 17 penetrating the inside of the earth shield pipe 31, unnecessary plasma is generated in the exhaust pipe 10 which is the exhaust path of the medium gas. Can be prevented. As a result, it is possible to prevent the consumption of high frequency power due to the generation of unnecessary plasma.
It is possible to increase the regular plasma generation efficiency inside and improve the coating speed of the carbon film.

(Example 2) As the internal electrode 18, a gas blow-out pipe 20 made of polytetrafluoroethylene and having an inner diameter of 1 mm was inserted into the bottom of a stainless piece-sealed tube having an outer diameter of 16 mm and a length of 70 mm shown in FIGS. The one with the worn structure was used.

This internal electrode 18 is replaced by the external electrode 6 shown in FIG.
Insert it in the plastic bottle B stored inside and use C as the medium.
₂ H ₂ gas, gas flow rate 20 sccm, gas pressure in PET bottle B and exhaust pipe 10 of 0.1 Torr, high high frequency supplied from high high frequency power supply of 100 MHz, bias high frequency power of bias power supply of 13 MHz Below, the inner surface of the PET bottle B was coated with a carbon film.

(Comparative Example 2) The outer diameter of the inner electrode was 16 m.
m, a carbon film was formed on the inner surface of the PET bottle B by the same method as in Example 2 except that one having a structure in which a single gas blowing hole having a hole diameter of 1 mm was drilled at the bottom of a stainless piece sealed tube having a length of 70 mm. Coated.

As a result, in Example 2, the inner surface of the PET bottle B was coated with the carbon film at a high speed. On the other hand, in Comparative Example 2, a film of black powder was formed on the inner surface of the bottom of the PET bottle B. It is considered that the formation of this black powder film is caused by the locally high density plasma generated by the concentration of the discharge near the gas blowing holes.

In the second embodiment, the gas blowing section made of the insulating material is composed of the gas blowing pipe 20 made of the insulating material shown in FIG. 5, but the present invention is not limited to this. For example, as shown in FIG. The gas blow-out portion made of is composed of a cap 22 made of an insulating material such as plastic or ceramic with a gas blow-out hole 21 opened in the direction of the central axis. You may attach to the bottom part of the electrode 18 so that it may connect with the said gas flow path 19. In the structure shown in FIG. 6, a gas blowing hole may be opened in the side wall of the cap 22.

(Third Embodiment) FIG. 7 is a sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to a third embodiment.

The cylindrical support member 42 having the flanges 41a and 41b at the upper and lower ends is mounted on the annular base 43. The cylindrical external electrode body 44 made of metal is arranged in the support member 42. A disc-shaped metal external electrode bottom member 45 is detachably attached to the bottom of the external electrode 44. The outer electrode body 44 and the outer electrode bottom member 45 constitute a bottomed cylindrical outer electrode 46 having a space in which a plastic container (for example, a PET bottle) B for forming a carbon coating can be installed. A disc-shaped insulator 47 is arranged between the base 43 and the external electrode bottom member 45.

The external electrode bottom member 45, the disk-shaped insulator 47, and the base 43 are moved up and down integrally with the external electrode body 4 by a pusher (not shown), and the external electrode body 4 Open and close the bottom.

The cylindrical spacer 49 made of a dielectric material has a cavity 48 having a shape of a combination of a cylinder and a truncated cone corresponding to the mouth and shoulder of the plastic bottle B to be inserted therein. The main body 4 in
It is inserted in the upper part of 4. The spacer 49 is fixed by a screw (not shown) screwed from an annular insulating member, which will be described later, placed on the spacer 49. In this way, the cylindrical spacer 49 is provided on the external electrode 46 in the main body 4
When the PET bottle B is inserted from the bottom side of the external electrode main body 44 by inserting and fixing it in the upper part of 4, the mouth and shoulder of the PET bottle B are placed in the cavity 48 of the spacer 49, and The plastic bottle B portion is housed in the external electrode 46.

The dielectric material forming the spacer 49 may be plastic or ceramic, for example. As the plastic, various types can be used, but a fluorine-based resin such as polytetrafluoroethylene, which has low high-frequency loss and excellent heat resistance, is particularly preferable. As the ceramic, alumina, steatite, which has a low high frequency loss, or macol, which has a high machinability, is preferable.

The annular insulating member 50 has an upper surface of the outer electrode 46 and an upper surface of the annular insulating member 50 which is the cylindrical support member 42.
Is placed so as to be flush with the upper flange 41a. The gas exhaust pipe 52 having upper and lower flanges 51 a and 51 b is mounted on the upper flange 41 a of the support member 42 and the upper surface of the annular insulating member 50. The exhaust pipe 52 is grounded. The gas exhaust pipe 52 is fixed to the support member 42 by screwing a screw (not shown) from the lower flange 51b of the exhaust pipe 52 to the upper flange 41a of the support member 42. In addition, a screw (not shown) penetrates the annular insulating portion 50 from the lower flange 51b of the exhaust pipe 52 and the main body 4 of the external electrode 46.
The exhaust pipe 52 is fixed to the annular insulating member 50 and the external electrode 46 by being screwed to
The annular insulating member 50 is also fixed to the external electrode 46. The exhaust pipe 52 and the annular insulating member 5
0 and the external electrode 46 are fixed by the exhaust pipe 52.
The external electrode 46 and the external electrode 46 have a mounting structure such that they are not electrically connected by a screw. The branch gas exhaust pipe 53 is connected to the side wall of the gas exhaust pipe 52, and an exhaust facility such as a vacuum pump (not shown) is attached to the other end thereof. The lid 54 is an upper flange 51a of the exhaust pipe 52.
Is attached to.

For example, a high frequency power source 55 which outputs a high frequency power having a frequency of 13.56 MHz is connected to the main body 44 of the external electrode 46 through a cable 56 and a power supply terminal 57. The matching device 58 is interposed in the cable 56 between the high frequency power supply 55 and the power supply terminal 57.

The gas supply pipe 59 penetrates the lid 54, and passes through the gas exhaust pipe 52 to form the main body 4 of the external electrode 46.
It is inserted in a portion corresponding to the mouth portion of the plastic bottle B in 4. Internal electrode 60 made of a metal having a substantially cylindrical shape
Is disposed near the bottom of the plastic bottle B inserted into the external electrode 46, and the upper end thereof is detachably attached to the lower end of the gas supply pipe 59. The internal electrode 6
A reference numeral 0 indicates that a gas flow path 61 is hollowed out in the central axis, and a gas blow-out tube 62 made of an insulating material such as plastic or ceramic, which is an insulating material for blowing out a medium gas, is provided at the bottom. It has been inserted.

The diameter of the internal electrode 60 is not more than the diameter of the mouthpiece of the bottle B.

The internal electrodes 60 are made of a heat-resistant metal material such as tungsten or stainless steel, but may be made of aluminum. If the surface of the internal electrode 60 is smooth, the carbon film deposited on the surface of the internal electrode 60 may be easily peeled off. Therefore, the surface of the internal electrode 60 is previously sandblasted,
It is preferable to increase the surface roughness to make it difficult for the carbon film deposited on the surface to peel off.

Next, a method for manufacturing an inner carbon film-covered plastic container using the carbon film forming apparatus shown in FIG. 7 will be described.

The external electrode bottom member 45, the disk-shaped insulator 47 and the base 43 are removed by a pusher (not shown) to open the bottom of the external electrode body 44. Subsequently, a plastic container, for example, a plastic bottle B is inserted from the bottom side of the opened external electrode body 44 from the mouth side of the bottle B, and then the external electrode bottom member 45 is attached to the bottom side of the external electrode body 44 by a pusher (not shown). By mounting the disk-shaped insulator 47 and the base 43 in this order, as shown in FIG. 7, the plastic bottle B is inserted into the cavity 48 of the cylindrical spacer 49 whose shoulder portion is made of a dielectric material. The bottle B is accommodated in the external electrode 46 from the shoulder side to the bottom side. At this time, the plastic bottle B is communicated with the exhaust pipe 52 through its mouth.

Next, the gas inside the exhaust pipe 52 and inside and outside the PET bottle B is exhausted through the branch exhaust pipe 53 and the exhaust pipe 52 by an exhaust means (not shown). Subsequently, the medium gas is supplied to the gas flow path 61 of the internal electrode 60 through the gas supply pipe 59, and is blown out into the plastic bottle B from the gas blowing pipe 62 made of an insulating material and attached to the bottom of the internal electrode 60. This medium gas further flows toward the mouth of the plastic bottle B. Then, the gas supply amount and the gas exhaust amount are balanced and the inside of the plastic bottle B is set to a predetermined gas pressure.

Next, high frequency power having a frequency of 13.56 MHz is supplied from the high frequency power supply 55 to the main body 44 of the external electrode 46 through the cable 56, the matching box 58 and the power supply terminal 57. At this time, plasma is generated around the internal electrode 60. Due to the generation of such plasma, the medium gas is dissociated by the plasma, and the inner surface of the PET bottle B in the external electrode 46 and the spacer 49 is coated with a uniform carbon film having a uniform thickness.

After the thickness of the carbon film reaches a predetermined thickness, the supply of high frequency power from the high frequency power supply 55 is stopped, the supply of medium gas is stopped, the residual gas is exhausted, and the gas is exhausted. After stopping, nitrogen, noble gas, air or the like is supplied into the PET bottle B through the gas supply pipe 59 and the gas flow passage 61 of the internal electrode 60 and the gas blowing pipe 62, and the inside and outside of the PET bottle B are brought to atmospheric pressure. Return and take out the inner carbon film-coated PET bottle. After that, the plastic bottle B is replaced according to the above-described order, and the next PET bottle coating operation is started.

As the medium gas, the same gas as in the first embodiment can be used.

The high frequency power is generally 13.56M.
However, the frequency is not limited to this.

As described above, according to the third embodiment, by supplying the medium gas into the plastic bottle B from the bottom of the internal electrode 60, the gas flow from the bottom of the plastic bottle B toward the mouth is forcibly generated. It can be done. Therefore, it is possible to prevent a gas retention portion from being formed in the plastic bottle B. As a result, the inner surface of the PET bottle B can be coated with a carbon film having a uniform film thickness with good film quality with less contamination.

Further, the medium gas is blown out from the gas blowing pipe 62 made of an insulating material inserted in the bottom portion of the internal electrode 60, so that the discharge is concentrated near the gas blowing pipe 62 as in the first embodiment. The density of the plasma generated in the PET bottle B can be made uniform by preventing it. As a result, the inner surface of the PET bottle B can be coated with a carbon film having a good film quality with less powder mixture and a uniform film thickness.

Furthermore, a cylindrical spacer 49 made of a dielectric material having a cavity 48 is inserted and fixed on the upper portion of the external electrode 46, so that the inner surface of the plastic bottle B from the shoulder portion to the bottom portion side in generating the plasma. Not only that, the carbon film having a uniform thickness can be coated from the mouth of the plastic bottle B facing the spacer 49 made of the dielectric material to the inner surface of the shoulder.

Therefore, it is possible to mass-produce an inner carbon film-coated PET bottle having an excellent barrier property which prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water).

Although the shape of the members covering the mouth and shoulders of the PET bottle B is complicated, the spacers 49 corresponding to these members are formed of a dielectric material such as plastic that can be injection-molded. As a result, it is possible to easily manufacture the device including all the members including the external electrodes as in the conventional case. Further, the weight of the entire device can be reduced as compared with the conventional case where all of these members and the like are constituted by the external electrodes made of a conductive material such as metal.

Further, by forming the spacer 49 from a dielectric material such as plastic or soft ceramic, it is possible to prevent damage to the complicated mouth and shoulder of the plastic bottle B when they come into contact with each other. can do.

In the third embodiment, the gas blowing section made of an insulating material is composed of the gas blowing pipe 62 made of an insulating material shown in FIG. 7, but the present invention is not limited to this. For example, as shown in FIGS. A similar structure, that is, a gas blowing portion made of an insulating material is composed of a cap made of an insulating material such as plastic or ceramic with gas blowing holes opened in the central axis direction. It may be hollowed out and attached to the bottom of the internal electrode so as to communicate with the gas passage. In such a structure, a gas blowing hole may be opened in the side wall of the cap.

In the third embodiment, the cylindrical spacer 49 made of a dielectric material having the cavity 48 is provided as the external electrode 46.
Although the plastic bottle B was inserted and fixed to the upper part of the plastic bottle B from the mouth to the shoulder, a thin film made of a dielectric material may be extended from the shoulder of the plastic bottle B to the bottom. .

(Fourth Embodiment) FIG. 8 is a sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to the fourth embodiment. In FIG. 8, the same members as those in FIG. 7 referred to in the third embodiment described above are designated by the same reference numerals, and the description thereof will be omitted.

This carbon film forming apparatus comprises a bias power source 6
3 is connected to the external electrode body 44 of the external electrode 46 through the cable 64 and the power supply terminal 65. Matching device 66
Is interposed in the cable 64 between the bias power source 63 and the power supply terminal 65.

The lid 54, which has an insulating ring 67 in the center and is grounded, is airtightly fixed to the upper flange 51a of the gas exhaust pipe 52. The housing 68 is attached on the lid 54.

The gas supply pipe 59 also serves as a terminal for high-frequency power, and serves as an insulating ring 6 for the lid 54 from the inside of the housing 68.
7 and is inserted into the spacer 49 in the external electrode 46 through the gas exhaust pipe 52. The upper end of the gas supply pipe 59 is connected to the lower end of a gas introduction pipe 69 that is inserted from the outside through the housing 68 via an insulating joint 70.

Flange pipe 71 and this flange pipe 71
The earth shield pipe 72 connected to the lower end is arranged so as to cover the gas exhaust pipe 52 and the gas supply pipe 59 portion located in the spacer 49. The earth shield pipe 72 is located inside the spacer 49 and inside the gas exhaust pipe 52 near the spacer 49. The upper end of the flange pipe 71 is connected to the back surface of the lid 54. That is, the earth shield pipe 72 is connected to the grounded lid 54 through the flange pipe 71.

The high-frequency power source 73 is connected to the side surface of the gas supply pipe 59 which also functions as a terminal for high-frequency power, through a cable 74 and a power supply terminal 75. Matching device 76
Is interposed in the cable 74 between the high frequency power supply 73 and the power supply terminal 75.

Next, a method for manufacturing an inner carbon film-covered plastic container using the carbon film forming apparatus shown in FIG. 8 will be described.

The external electrode bottom member 45, the disc-shaped insulator 47 and the base 43 are removed by a pusher (not shown) to open the bottom of the external electrode body 44. Subsequently, a plastic container, for example, a plastic bottle B is inserted from the bottom side of the opened external electrode body 44 from the mouth side of the bottle B, and then the external electrode bottom member 45 is attached to the bottom side of the external electrode body 44 by a pusher (not shown). By mounting the disk-shaped insulator 47 and the base 43 in this order, as shown in FIG. 8, the plastic bottle B is inserted into the cavity 48 of the cylindrical spacer 49 whose shoulder portion is made of a dielectric material. The bottle B is accommodated in the external electrode 46 from the shoulder side to the bottom side. At this time, the plastic bottle B is communicated with the exhaust pipe 52 through its mouth.

Next, the gas inside the exhaust pipe 52 and inside and outside the plastic bottle B is exhausted through the branch exhaust pipe 53 and the exhaust pipe 52 by an exhaust means (not shown). Subsequently, the medium gas is supplied to the gas flow path 62 of the internal electrode 61 through the gas introduction pipe 69 and the gas supply pipe 59, and the plastic bottle B is discharged from the gas blowing pipe 62 made of an insulating material and attached to the bottom of the internal electrode 61. Let it blow out. This medium gas further flows toward the mouth of the plastic bottle B. Then, the gas supply amount and the gas exhaust amount are balanced and the inside of the plastic bottle B is set to a predetermined gas pressure.

Next, bias power is supplied from the bias power source 63 to the external electrode 46 through the cable 64, the matching unit 66 and the power supply terminal 65. Thereafter or at the same time, high-frequency power is supplied from the high-frequency power supply 73 to the gas supply pipe 59 through the cable 74, the matching unit 76 and the power supply terminal 75, and the high-frequency power is supplied to the internal electrode 60 through the gas supply pipe 59. . At this time, plasma is generated around the internal electrode 60. Further, the earth shield pipe 72 is arranged on the outer circumference of the gas supply pipe 59 so as to be located inside the spacer 49 and inside the gas exhaust pipe 52 near the spacer 49, and is grounded through the flange pipe 71. A bias voltage can be applied from the external electrode 46 to the internal electrode 60, that is, to the generated plasma with the earth shield tube 72 as a reference potential.

As a result, a) When high high frequency power is used,
In particular, a high electron density can be obtained under low gas pressure conditions as compared with high frequency power, so the frequency of collisions with the medium gas increases and the density of film forming species can be increased. B) Adjusting the bias power changes the potential difference from the plasma potential. Therefore, the ion energy incident on the inner surface of the plastic bottle B can be adjusted,
c) Since the ion density is proportional to the electron density, the ion flux incident on the inner surface of the plastic bottle B can be controlled by using it together with the adjustment of the potential difference. By generating plasma and applying a bias voltage to the internal electrode 60, the plasma is drawn into the external electrode 46,
A film forming species obtained when the medium gas is dissociated by the plasma can be coated at a high speed with a uniform carbon film having a uniform thickness on the inner surface of the PET bottle B in the external electrode 46 to which the bias power is applied. .

After the thickness of the carbon film reaches a predetermined value, the bias power and the high frequency power from the bias power source 63 and the high frequency power source 73 are stopped, and the supply of the medium gas is stopped, and the residual gas remains. After exhausting the gas and stopping the exhaust of the gas, nitrogen, a noble gas, air or the like is introduced into the gas introducing pipe 6
9 through the gas supply pipe 59 through the gas flow path 61 of the internal electrode 60 and the gas blowing pipe 62
The inside of the plastic bottle B is returned to atmospheric pressure,
Take out the plastic bottle coated with the inner carbon film. After that, the plastic bottle B is replaced according to the above-described order, and the next PET bottle coating operation is started.

As the medium gas, the same gas as described in the first embodiment can be used.

The high-frequency power is generally 30 to 30.
It is defined as 0 MHz, but is not limited to this. Further, the application of these electric powers may be continuous or intermittent (pulse-like).

The bias power is generally 13.56.
Although the frequency band of 100 MHz to 1000 W is used, the frequency is not limited to this. Further, the application of the bias power may be continuous or intermittent (pulse-like).

As described above, according to the fourth embodiment, by supplying the medium gas into the plastic bottle B from the bottom of the internal electrode 60, a gas flow from the bottom of the plastic bottle B toward the mouth is forcibly generated. It can be done. Therefore, it is possible to prevent a gas retention portion from being formed in the plastic bottle B. As a result, the inner surface of the PET bottle B can be coated with a carbon film having a uniform film thickness with good film quality with less contamination.

Further, the medium gas is blown out from the gas blowing pipe 62 made of an insulating material inserted in the bottom of the internal electrode 60, so that the discharge is concentrated near the gas blowing pipe 62 as in the first embodiment. The density of the plasma generated in the PET bottle B can be made uniform by preventing it. As a result, the inner surface of the PET bottle B can be coated with a carbon film having a good film quality with less powder mixture and a uniform film thickness.

Furthermore, bias power is applied to the film forming species obtained when the medium gas is dissociated by the plasma by generating plasma and drawing the plasma to the external electrode 46 by applying the bias voltage to the internal electrode 60. The inner surface of the PET bottle B in the external electrode 46 thus formed can be coated at a high speed with a uniform carbon film having a uniform thickness.

Therefore, it is possible to mass-produce the inner carbon film-coated PET bottle having an excellent barrier property, which prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water).

Further, between the gas supply pipe 59 to which high-frequency power is applied and the exhaust pipe 52 which is grounded (that is, the exhaust pipe 5).
Similarly, in (2), unnecessary plasma is generated and the coating efficiency of the carbon film is reduced. For this reason, the earth shield pipe 72 is arranged on the outer circumference of the gas supply pipe 59 so as to be located in the gas exhaust pipe 52 near the mouth of the plastic bottle B, and the flange for supporting the earth shield pipe 72. By grounding through the pipe 71, even if high-frequency power is supplied to the gas supply pipe 59 penetrating through the earth shield pipe 72, unnecessary plasma is generated in the exhaust pipe 52 that is the exhaust path of the medium gas. Can be prevented. As a result, it is possible to prevent the consumption of high frequency power due to the generation of unnecessary plasma.
It is possible to increase the regular plasma generation efficiency inside and improve the coating speed of the carbon film.

Further, although the shape of the members covering the mouth and shoulders of the PET bottle B is complicated, the spacers 49 corresponding to these members are made of a dielectric material such as injection moldable plastic such as plastic. By
It can be manufactured more easily than in the conventional case where all of these members are formed of external electrodes. Moreover,
It is possible to reduce the weight of the entire device as compared with the conventional case where all of these members are made of a conductive material such as metal with external electrodes. In addition, by forming the spacer 49 from a dielectric material such as plastic or soft ceramic, it is possible to prevent damage to the complicated mouth and shoulder of the plastic bottle B when they come into contact with each other. You can

In the fourth embodiment, the gas blowing portion made of an insulating material is composed of the gas blowing pipe 62 made of an insulating material shown in FIG. 8. However, the present invention is not limited to this. For example, as shown in FIGS. A similar structure, that is, a gas blowing portion made of an insulating material is composed of a cap made of an insulating material such as plastic or ceramic with gas blowing holes opened in the central axis direction. It may be hollowed out and attached to the bottom of the internal electrode so as to communicate with the gas passage. In such a structure, a gas blowing hole may be opened in the side wall of the cap.

In the fourth embodiment, the columnar spacer 49 made of a dielectric material having the cavity 48 is used as the external electrode 4.
6 was inserted and fixed so as to correspond to the shoulder portion from the mouth of the PET bottle B, but a thin film made of a dielectric material may be extended from the shoulder portion of the PET bottle B to the bottom portion. Good.

(Fifth Embodiment) FIG. 9 is a sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to a fifth embodiment, and FIG. 10 is an enlarged sectional view showing the vicinity of the internal electrodes in FIG.

The cylindrical support member 82 having the flanges 81a and 81b at the upper and lower ends is placed on the annular base 83. The tubular external electrode body 84 made of metal is disposed inside the support member 82. A disk-shaped metal external electrode bottom member 85 is detachably attached to the bottom of the external electrode 84. The outer electrode body 84 and the outer electrode bottom member 85 constitute a bottomed cylindrical outer electrode 86 having a space in which a plastic container (for example, a PET bottle) B forming a carbon coating can be installed. The disc-shaped insulator 87 is arranged between the base 83 and the external electrode bottom member 85.

The external electrode bottom member 85, the disc-shaped insulator 87 and the base 83 are integrally moved up and down with respect to the external electrode main body 84 by a pusher (not shown), and the external electrode main body 84 Open and close the bottom.

The annular insulating member 88 has the upper surface of the outer electrode 86 and the upper surface of the annular insulating member 88, which is the cylindrical support member 82.
Is placed so as to be flush with the upper flange 81a. The gas exhaust pipe 90 having upper and lower flanges 89a and 89b is placed on the upper flange 81a of the support member 82 and the upper surface of the annular insulating member 88. The exhaust pipe 90 is grounded. The gas exhaust pipe 90 is fixed to the support member 82 by screwing a screw (not shown) from the lower flange 89b of the exhaust pipe 90 to the upper flange 81a of the support member 82. Further, a screw (not shown) penetrates the annular insulating portion 88 from the lower flange 89b of the exhaust pipe 90 and the main body 8 of the external electrode 86.
The exhaust pipe 90 is fixed to the annular insulating member 88 and the external electrode 86 by being screwed to
The annular insulating member 88 is also fixed to the external electrode 86. The exhaust pipe 90 and the annular insulating member 8
8 and the external electrode 86 are fixed to the exhaust pipe 90.
The external electrode 86 and the external electrode 86 have a mounting structure such that they are not electrically connected by a screw. The branch gas exhaust pipe 91 is connected to the side wall of the gas exhaust pipe 90, and an exhaust facility such as a vacuum pump (not shown) is attached to the other end.

The bias power source 92 is connected to the external electrode body 8 of the external electrode 86 through the cable 93 and the power supply terminal 94.
4 is connected. The matching unit 95 is interposed in the cable 93 between the bias power source 92 and the power supply terminal 94.

The lid 97, which has an insulating ring 96 at its center and is grounded, is the upper flange 89 of the gas exhaust pipe 90.
It is airtightly fixed to a. The housing 98 is attached on the lid 97.

Gas introduction pipe 99 for introducing the medium gas
Is inserted into the housing 98 from the outside. The gas supply pipe 100 also serves as a terminal for high-frequency power, and serves as the housing 9
8 through the insulating ring 96 of the lid 97, and through the gas exhaust pipe 90 into the main body 84 of the external electrode 86 (in the portion corresponding to the central portion of the PET bottle B to be inserted). There is. The upper end of the gas supply pipe 100 is connected to the lower end of the gas introduction pipe 99 via an insulating joint 101.

Internal electrode 102 made of a metal having a substantially cylindrical shape
Is disposed near the bottom of the PET bottle B inserted in the external electrode 86, and the upper end thereof is the gas supply pipe 100.
It is detachably attached to the lower end of. The internal electrode 102 has a gas flow path 103 cut out in the central axis, and a cap 105 having a gas blowing hole 104 for blowing out a medium gas at the bottom is detachably attached.

The diameter of the internal electrode 102 is equal to or smaller than the diameter of the base of the bottle B.

The internal electrodes 102 are made of a heat-resistant metal material such as tungsten or stainless steel, but may be made of aluminum. If the surface of the internal electrode 102 is smooth, the internal electrode 102
There is a possibility that the carbon film deposited on the surface of the may be easily peeled off. Therefore, it is preferable that the surface of the internal electrode 102 is previously sandblasted to increase the surface roughness so that the carbon film deposited on the surface is difficult to peel off.

Flange tube 106 and this flange tube 1
The earth shield pipe 107 connected to the lower end of 06 covers the gas exhaust pipe 90 and the portion of the gas supply pipe 100 located inside the body 84 of the external electrode 86 corresponding to the center of the plastic bottle B. It is located in.

The lower end of the earth shield tube 107 is arranged with a desired gap g from the upper end of the internal electrode 102, as shown in FIGS. 9 and 10. The length of this gap g is preferably 20 to 30 mm. Insulation tube 1 made of plastics such as polytetrafluoroethylene, polypropylene
Reference numeral 08 denotes the internal electrode 102 and the earth shield tube 107.
Is entirely covered, including the gas supply pipe 100 located in a region (region of the gap g) separated from the lower end of the.

The upper end of the flange tube 106 is connected to the back surface of the lid body 97. That is, the earth shield pipe 107 is connected to the lid 97 that is grounded through the flange pipe 106.

The high-frequency power supply 109 is connected to the side surface of the gas supply pipe 100, which also functions as a terminal for high-frequency power, through a cable 110 and a power supply terminal 111. The matching unit 112 includes the high-frequency power source 109 and the power supply terminal 1.
It is interposed in the cable 110 between 11.

Next, a method of manufacturing an inner carbon film-covered plastic container using the carbon film forming apparatus shown in FIG. 9 will be described.

The external electrode bottom member 85, the disk-shaped insulator 87 and the base 83 are removed by a pusher (not shown) to open the bottom of the external electrode body 84. Subsequently, a plastic container, for example, a plastic bottle B is inserted from the bottom side of the opened external electrode body 84 from the mouth side of the bottle B, and then the external electrode bottom member 85 is attached to the bottom side of the external electrode body 84 by a pusher (not shown). By mounting the disk-shaped insulator 87 and the base 83 in this order, the PET bottle B is placed in the internal space of the external electrode 86 including the external electrode body 4 and the external electrode bottom member 5 as shown in FIG. Store. At this time, the plastic bottle B is attached to the exhaust pipe 9
0 through its mouth.

Next, the gas inside and outside the exhaust pipe 90 and the plastic bottle B is exhausted through the branch exhaust pipe 91 and the exhaust pipe 90 by an exhaust means (not shown). Subsequently, the medium gas is introduced into the gas introduction pipe 99 and the gas supply pipe 100.
Gas is supplied to the gas flow path 103 of the internal electrode 102 through the gas flow hole 104 of the cap 105 attached to the bottom of the internal electrode 102 and blown into the plastic bottle B. This medium gas further flows toward the mouth of the plastic bottle B. Then, the gas supply amount and the gas exhaust amount are balanced and the inside of the plastic bottle B is set to a predetermined gas pressure.

Next, bias power is supplied from the bias power source 92 to the external electrode 86 through the cable 93, the matching box 95 and the power supply terminal 94. Thereafter or at the same time, the high-frequency power supply 109 supplies high-frequency power to the gas supply pipe 100 through the cable 110, the matching unit 112, and the power supply terminal 111.
High-frequency power is supplied to the internal electrode 102 through. At this time, plasma is generated around the internal electrode 102. Further, since the exhaust pipe 90 located above the external electrode 86 is grounded, a bias voltage is applied from the external electrode 86 to the internal electrode 1 with the exhaust pipe 90 as a reference potential.
02, i.e. towards the generated plasma.

As a result, a) When high high frequency power is used,
In particular, a high electron density can be obtained under low gas pressure conditions as compared with high frequency power, so the frequency of collisions with the medium gas increases and the density of film forming species can be increased. B) Adjusting the bias power changes the potential difference from the plasma potential. Therefore, the ion energy incident on the inner surface of the plastic bottle B can be adjusted,
c) Since the ion density is proportional to the electron density, the ion flux incident on the inner surface of the plastic bottle B can be controlled by using it together with the adjustment of the potential difference. Bias power was applied to the film formation species obtained when the medium gas was dissociated by the plasma due to the generation of the plasma and the drawing of the plasma to the outer electrode 86 by applying the bias voltage to the inner electrode 102. A uniform carbon film having a uniform thickness can be coated on the inner surface of the PET bottle B in the external electrode 86 at a high speed.

However, when high-frequency power is supplied from the high-frequency power supply 109 to the gas supply pipe 100, unnecessary plasma is similarly generated between the gas supply pipe 100 and the grounded exhaust pipe 90 (that is, inside the exhaust pipe 90), and carbon is generated. The coating efficiency of the membrane is reduced. As a countermeasure against this, the earth shield pipe 107 is arranged on the outer circumference of the gas supply pipe 100, and the earth shield pipe 107 is grounded through the flange pipe 106 that supports the earth shield pipe 107 so that the gas supply penetrating the inside of the earth shield pipe 107. Even if high-frequency power is supplied to the tube 100, generation of unnecessary plasma is prevented in the exhaust tube 90, which is the exhaust path of the medium gas. As a result, it is possible to prevent consumption of high-frequency power due to unnecessary plasma generation, so that the regular plasma generation efficiency in the plastic bottle B can be improved.

By disposing the earth shield pipe 107 on the outer periphery of the gas supply pipe 100, unnecessary plasma generation can be prevented, but on the other hand, the earth shield pipe 10
7 discharge occurs between the lower end and the upper end of the internal electrode 102 to which high-frequency power is supplied, and the plasma density at that portion increases, so that contamination (powder) is mixed into the inner surface of the PET bottle B and the film thickness is It becomes uneven. As a countermeasure against this, the lower end of the earth shield tube 107 is arranged with a desired gap g from the upper end of the internal electrode 102 as shown in FIGS. 9 and 10, and the insulating tube 108 is provided at least to the internal electrode 102 and the earth shield. By covering the portion of the gas supply pipe 100 located in a region separated from the lower end of the pipe 107 (the region of the gap g), the discharge at the location is prevented and the density of the plasma generated in the PET bottle B. Are made uniform.

After the thickness of the carbon film reaches a predetermined value, the bias power and the high-frequency power supplied from the bias power source 92 and the high-frequency power source 109 are stopped, and the supply of the medium gas is stopped. After exhausting the gas and stopping the exhaust of the gas, nitrogen, rare gas, air or the like is passed from the gas introduction pipe 99 through the gas supply pipe 100 through the gas flow path 103 of the internal electrode 102 and the gas blowing hole 104 to the PET bottle. Then, the inside and outside of the plastic bottle B are returned to atmospheric pressure, and the internal carbon film-coated plastic bottle is taken out. After that, change the plastic bottle B according to the order described above,
Move on to the next PET bottle coating operation.

The medium gas is basically a hydrocarbon, for example, alkanes such as methane, ethane, propane, butane, pentane and hexane; ethylene, propylene,
Alkenes such as butene, pentene and butadiene; alkynes such as acetylene; benzene, toluene, xylene,
Aromatic hydrocarbons such as indene, naphthalene and phenanthrene; cycloparaffins such as cyclopropane and cyclohexane; cycloolefins such as cyclopentene and cyclohexene; oxygen-containing hydrocarbons such as methyl alcohol and ethyl alcohol; methylamine, ethylamine,
Nitrogen-containing hydrocarbons such as aniline can be used, and carbon monoxide, carbon dioxide, etc. can also be used.

The high high frequency power is generally 30 to 30.
It is defined as 0 MHz, but is not limited to this. Further, the application of these electric powers may be continuous or intermittent (pulse-like).

The bias power is generally 13.56.
Although the frequency band of 100 MHz to 1000 W is used, the frequency is not limited to this. Further, the application of the bias power may be continuous or intermittent (pulse-like).

As described above, according to the fifth embodiment, when the medium gas is dissociated by the plasma by the generation of the plasma and the drawing of the plasma to the external electrode 86 by the application of the bias voltage to the internal electrode 102, the production is obtained. A uniform carbon film having a uniform thickness can be coated at a high speed on the inner surface of the plastic bottle B in the external electrode 86 to which the bias power is applied.

Further, the earth shield pipe 107 is arranged on the outer circumference of the gas supply pipe 100, and the earth shield pipe 107 is grounded through the flange pipe 106 that supports the gas. Even if high-frequency power is supplied to 100, it is possible to prevent unnecessary plasma from being generated in the exhaust pipe 90, which is the exhaust path of the medium gas. As a result, it is possible to prevent consumption of high-frequency power due to unnecessary plasma generation, so that the regular plasma generation efficiency in the PET bottle B can be increased and the coating speed of the carbon film can be improved.

Further, the lower end of the earth shield tube 107 is arranged with a desired gap g from the upper end of the internal electrode 102, and the insulating tube 108 is at least separated from the internal electrode 102 and the lower end of the earth shield tube 107. By covering the gas supply pipe 100 located in the region (region of the gap g), the lower end of the earth shield pipe 107 and the internal electrode 10 to which high-frequency power is supplied.
Since a discharge can be prevented from being generated between the upper end and the upper end, a carbon film having a uniform film thickness in which a plasma having a uniform density can be generated in the PET bottle B and powder is not mixed in the inner surface thereof is good Can be coated.

Therefore, it is possible to mass-produce an inner carbon film-coated PET bottle having an excellent barrier property which prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water).

(Sixth Embodiment) FIG. 11 is a sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to the sixth embodiment. In addition, in FIG.
The same members as those in FIG. 9 referred to in the embodiment are designated by the same reference numerals and the description thereof will be omitted.

In this carbon film forming apparatus, the structure for storing the PET bottle B has a spacer 114 having a cavity 113 for covering the mouth and shoulder of the PET bottle B, and an external electrode body 115 for covering the other PET bottle B portion. And an external electrode 117 composed of the external electrode bottom member 116.

Next, a method of manufacturing an inner carbon film-covered plastic container using the carbon film forming apparatus shown in FIG. 11 will be described.

The external electrode bottom member 85, the disc-shaped insulator 87 and the base 83 are removed by a pusher (not shown) to open the bottom of the external electrode body 84. Subsequently, a plastic container, for example, a plastic bottle B is inserted from the bottom side of the opened external electrode body 84 from the mouth side of the bottle B, and then the external electrode bottom member 85 is attached to the bottom side of the external electrode body 84 by a pusher (not shown). , The disk-shaped insulator 87 and the base 83 are attached in this order,
As shown in, inside the cavity 113 of the cylindrical spacer 114 whose shoulder portion from the mouth portion of the plastic bottle B is made of a dielectric material,
The bottle B is accommodated in the external electrode 117 from the shoulder side to the bottom side. At this time, the plastic bottle B is communicated with the exhaust pipe 90 through its mouth.

Next, the gas inside and outside the exhaust pipe 90 and the plastic bottle B is exhausted through the branch exhaust pipe 91 and the exhaust pipe 90 by an exhaust means (not shown). Subsequently, the medium gas is introduced into the gas introduction pipe 99 and the gas supply pipe 100.
Gas is supplied to the gas flow path 103 of the internal electrode 102 through the gas flow hole 104 of the cap 105 attached to the bottom of the internal electrode 102 and blown into the plastic bottle B. This medium gas further flows toward the mouth of the plastic bottle B. Then, the gas supply amount and the gas exhaust amount are balanced and the inside of the plastic bottle B is set to a predetermined gas pressure.

Next, bias power is supplied from the bias power source 92 to the external electrode 86 through the cable 93, the matching box 95 and the power supply terminal 94. Thereafter or at the same time, the high-frequency power supply 109 supplies high-frequency power to the gas supply pipe 100 through the cable 110, the matching unit 112, and the power supply terminal 111.
High-frequency power is supplied to the internal electrode 102 through. At this time, plasma is generated around the internal electrode 102. Further, the earth shield tube 107 is the spacer 1
14 is located on the outer circumference of the gas supply pipe 100 so as to be located inside the gas exhaust pipe 90 near the spacer 114, and is grounded through the flange pipe 106, the earth shield pipe 107 is used as a reference potential. A bias voltage is applied from the external electrode 86 to the internal electrode 10
It can be applied towards 2, i.e. towards the generated plasma.

As a result, a) When high high frequency power is used,
In particular, a high electron density can be obtained under low gas pressure conditions as compared with high frequency power, so the frequency of collisions with the medium gas increases and the density of film forming species can be increased. B) Adjusting the bias power changes the potential difference from the plasma potential. Therefore, the ion energy incident on the inner surface of the plastic bottle B can be adjusted,
c) Since the ion density is proportional to the electron density, the ion flux incident on the inner surface of the plastic bottle B can be controlled by using it together with the adjustment of the potential difference. Bias power was applied to the film formation species obtained when the medium gas was dissociated by the plasma due to the generation of the plasma and the drawing of the plasma to the outer electrode 86 by applying the bias voltage to the inner electrode 102. A uniform carbon film having a uniform thickness can be coated on the inner surface of the PET bottle B in the external electrode 86 at a high speed.

After the thickness of the carbon film reaches a predetermined value, the bias power supply and the high-frequency power supply from the bias power supply 92 and the high-frequency power supply 109 are stopped, the supply of the medium gas is stopped, and the residual gas remains. After exhausting the gas and stopping the exhaust of the gas, nitrogen, rare gas, air or the like is passed from the gas introduction pipe 99 through the gas supply pipe 100 through the gas flow path 103 of the internal electrode 102 and the gas blowing hole 104 to the PET bottle. Then, the inside and outside of the plastic bottle B are returned to atmospheric pressure, and the internal carbon film-coated plastic bottle is taken out. After that, change the plastic bottle B according to the order described above,
Move on to the next PET bottle coating operation.

As the medium gas, the same gas as described in the fifth embodiment can be used.

The high high frequency power is generally 30 to 30.
It is defined as 0 MHz, but is not limited to this. Further, the application of these electric powers may be continuous or intermittent (pulse-like).

The bias power is generally 13.56.
Although the frequency band of 100 MHz to 1000 W is used, the frequency is not limited to this. Further, the application of the bias power may be continuous or intermittent (pulse-like).

As described above, according to the sixth embodiment, when the medium gas is dissociated by the plasma by the generation of the plasma and the drawing of the plasma to the external electrode 86 by the application of the bias voltage to the internal electrode 102, the manufacturing method is obtained. A uniform carbon film having a uniform thickness can be coated at a high speed on the inner surface of the plastic bottle B in the external electrode 86 to which the bias power is applied.

Further, by disposing the earth shield pipe 107 on the outer circumference of the gas supply pipe 100 and grounding the earth shield pipe 107 through the flange pipe 106 supporting the same, as described in detail in the fifth embodiment, Even if high-frequency power is supplied to the gas supply pipe 100 penetrating the earth shield pipe 107, unnecessary plasma can be prevented from being generated in the exhaust pipe 90 that is an exhaust path of the medium gas. As a result, it is possible to prevent consumption of high-frequency power due to unnecessary plasma generation, so that the regular plasma generation efficiency in the PET bottle B can be increased and the coating speed of the carbon film can be improved.

Further, the lower end of the earth shield tube 107 is arranged with a desired gap g from the upper end of the internal electrode 102, and the insulating tube 108 is at least separated from the internal electrode 102 and the lower end of the earth shield tube 107. As described in detail in the fifth embodiment, by covering the portion of the gas supply pipe 100 located in the region (region of the gap g), the lower end of the earth shield pipe 107 and the upper end of the internal electrode 102 to which high-frequency power is supplied. Since a discharge can be prevented from occurring between the inside and the inside of the plastic bottle B, a plasma having a uniform density can be generated, and the inner surface thereof is covered with a carbon film having a good film quality with little powder inclusion and a uniform film thickness. can do.

Therefore, it is possible to mass-produce an inner carbon film-coated PET bottle having an excellent barrier property, which prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water).

Although the shape of the members covering the mouth and shoulders of the PET bottle B is complicated, the spacers 114 corresponding to these members are formed of a dielectric material such as plastic that can be injection-molded. By
It can be manufactured more easily than in the conventional case where all of these members are formed of external electrodes. Moreover,
It is possible to reduce the weight of the entire device as compared with the conventional case where all of these members are made of a conductive material such as metal with external electrodes. In addition, the spacer 114 is formed of a dielectric material such as plastic or soft ceramic to prevent damage to the complicated mouth and shoulder of the plastic bottle B when they come into contact with each other. You can

In the sixth embodiment, the hollow portion 113
Although the cylindrical spacer 114 made of a dielectric material having the above is inserted and fixed to the upper portion of the external electrode 86 so as to correspond to the mouth portion and the shoulder portion of the PET bottle B, the shoulder portion of the PET bottle B is further extended to the bottom portion. A thin film made of a dielectric material may be extended.

[0180]

As described above in detail, according to the present invention, a carbon film forming apparatus for forming an inner surface of a plastic container, which has a good film quality and can coat a carbon film having a uniform thickness, on the inner surface of the plastic container. Can be provided.

Further, according to the present invention, there is provided a method capable of producing a plastic container having a good film quality and having a uniform film thickness coated on the inner surface thereof and having an excellent barrier property against oxygen and carbon dioxide. You can

Further, according to the present invention, there is provided an apparatus for forming a carbon film on the inner surface of a plastic container, which has a good film quality on the inner surface of the plastic container and can coat a carbon film having a uniform thickness at a high speed. You can

Further, according to the present invention, a carbon film having a good film quality and a uniform film thickness is coated on the inner surface at a high speed, and a plastic container having an excellent barrier property against oxygen and carbon dioxide is mass-produced. A method of obtaining can be provided.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an apparatus for forming a carbon film on an inner surface of a plastic container according to a first embodiment of the present invention.

FIG. 2 is an enlarged cross-sectional view showing an internal electrode of FIG.

FIG. 3 is a cross-sectional view showing a modified example of the internal electrode incorporated in the carbon film forming device for the inner surface of the plastic container according to the first embodiment of the present invention.

FIG. 4 is a cross-sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to a second embodiment of the present invention.

5 is an enlarged cross-sectional view showing an internal electrode of FIG.

FIG. 6 is a cross-sectional view showing a modified example of the internal electrode incorporated in the carbon film forming device for the inner surface of the plastic container according to the second embodiment of the present invention.

FIG. 7 is a sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to a third embodiment of the present invention.

FIG. 8 is a sectional view showing an apparatus for forming a carbon film on an inner surface of a plastic container according to a fourth embodiment of the present invention.

FIG. 9 is a sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to a fifth embodiment of the present invention.

10 is an enlarged cross-sectional view showing the vicinity of the internal electrodes of FIG.

FIG. 11 is a sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to a sixth embodiment of the present invention.

FIG. 12 is a cross-sectional view showing a conventional carbon film forming device on the inner surface of a plastic container.

[Explanation of symbols]

2, 42, 82 ... Support member, 4, 44, 84, 115 ... External electrode body, 5, 45, 85, 116 ... External electrode bottom member, 6, 46, 86, 117 ... External electrodes, 10, 52, 90 ... Exhaust pipe, 13, 55 ... High frequency power supply, 17, 59, 100 ... Gas supply pipe, 18, 60, 102 ... Internal electrodes, 20, 62 ... Gas blow-out pipe, 21 ... Gas blowing hole, 22 ... a cap made of an insulating material, 23, 63, 92 ... Bias power supply, 31, 72, 107 ... Earth shield tube, 32, 73, 109 ... High-frequency power supply, 49, 114 ... Cylindrical spacer, 108 ... Insulation tube, B ... PET bottle,

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Mitsuo Kato             1-8 Koura, Kanazawa-ku, Yokohama-shi, Kanagawa               Mitsubishi Heavy Industries, Ltd. Basic Technology Research Center (72) Inventor Yuji Asahara             4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture               Mitsubishi Heavy Industries Ltd. Hiroshima Research Center F-term (reference) 3E062 AA09 AB02 AC02 JA01 JA07                       JB24 JC01 JD01                 4K030 BA27 CA07 CA15 FA03 JA09                       KA12 KA14 KA16 KA17 KA20

Claims (13)

[Claims] 1. An external electrode having a size that surrounds an outer circumference of a plastic container, which is an object to be processed, and an insulating member on an end surface of the external electrode on a side where a mouth portion of the container is located. An exhaust pipe attached via the exhaust pipe, an internal electrode inserted into the plastic container in the external electrode from the exhaust pipe side and connected to a ground side, an exhaust unit attached to the exhaust pipe, the internal A gas supply means for supplying a medium gas to the electrodes; and a high frequency power source connected to the external electrodes, wherein the internal electrodes are located on the bottom side of the plastic container inserted into the external electrodes. An apparatus for forming a carbon film on the inner surface of a plastic container, characterized in that a gas blow-out portion made of an insulating material for blowing out a medium gas is provided on the inside. 2. When manufacturing an inner carbon film-covered plastic container using the carbon film forming apparatus according to claim 1, (a) a step of inserting the plastic container, which is the object to be treated, into an external electrode; b) An internal electrode provided with a gas blowing portion made of an insulating material is introduced into the inside of the plastic container from an exhaust pipe attached to an end surface of the external electrode on the side where the mouth of the container is located via an insulating member. Inserting the gas outlet so that the gas outlet is located on the bottom side of the container, and (c) exhausting gas inside and outside the container through the exhaust pipe by exhaust pipe means, and then supplying medium gas to the internal electrode. And supplying a medium gas into the plastic container from the gas outlet of the internal electrode to set the exhaust pipe including the inside of the plastic container to a predetermined gas pressure. (D) supplying high frequency power from a high frequency power source to the external electrodes to generate plasma around the internal electrodes located in the plastic container, and the plasma dissociates the medium gas to disperse the plastic gas; And a step of coating the inner surface of the container with a carbon film. 3. An external electrode having a size that surrounds a plastic container, which is an object to be processed, when the container is inserted, and an end face of the external electrode on the side where the mouth of the container is located, with an insulating member interposed therebetween. An exhaust pipe attached, an internal electrode inserted from the exhaust pipe side into the plastic container in the external electrode, an exhaust unit attached to the exhaust pipe, and for supplying a medium gas to the internal electrode Gas supply means, a high-frequency power supply connected to the internal electrode, and a bias power supply connected to the external electrode, wherein the internal electrode is a bottom portion of a plastic container inserted into the external electrode. An apparatus for forming a carbon film on the inner surface of a plastic container, characterized in that a gas blow-out portion made of an insulating material for blowing out a medium gas is provided in a portion located on the side. 4. When manufacturing an inner surface carbon film-coated plastic container using the carbon film forming apparatus according to claim 3, (a) a step of inserting the plastic container, which is the object to be treated, into the external electrode, b) An internal electrode provided with a gas blowing portion made of an insulating material is introduced into the inside of the plastic container from an exhaust pipe attached to an end surface of the external electrode on the side where the mouth of the container is located via an insulating member. Inserting the gas outlet so that the gas outlet is located on the bottom side of the container, and (c) exhausting gas inside and outside the container through the exhaust pipe by exhaust pipe means, and then supplying medium gas to the internal electrode. And supplying a medium gas into the plastic container from the gas outlet of the internal electrode to set the exhaust pipe including the inside of the plastic container to a predetermined gas pressure. (D) applying high-frequency power from the bias power supply to the external electrode, and supplying high-frequency power from the high-frequency power supply to the internal electrode through the gas supply pipe to generate plasma in the plastic container. And a step of dissociating the medium gas by the plasma to coat the carbon film on the inner surface of the plastic container. 5. An external electrode having a size that surrounds a container to be processed when it is inserted, and at least a mouth and a shoulder of the container when the container to be processed is inserted. A spacer made of a dielectric material interposed between the external electrode and the external electrode; an exhaust pipe attached to the end surface of the external electrode on the side where the mouth of the container is located via an insulating member; An internal electrode inserted into the plastic container from the exhaust pipe side and connected to the ground side; an exhaust means attached to the exhaust pipe; and a gas supply means for supplying a medium gas to the internal electrode. A high frequency power source connected to the external electrode, wherein the internal electrode blows a medium gas to a portion located on the bottom side of the plastic container inserted into the external electrode. Carbon film forming apparatus of the plastic container inner surface, wherein a gas blowout unit made of an insulating material Sutame is provided. 6. When manufacturing an inner carbon film-covered plastic container using the carbon film forming apparatus according to claim 5, (a) a plastic container, which is an object to be treated, is formed in an outer electrode and a spacer made of a dielectric material. At least the outer periphery of the mouth and shoulder of the container is surrounded by the spacer, and the outer periphery of the other container part is surrounded by the external electrode, and (b) from an insulating material An internal electrode provided with a gas blowout part, the gas blowout part inside the plastic container from an exhaust pipe attached to the end surface of the external electrode on the side where the mouth of the container is located via an insulating member. Inserting the container so as to be located on the bottom side, and (c) exhausting gas inside and outside the container through the exhaust pipe by exhaust pipe means, and then supplying medium gas to the internal electrode. Is supplied by a gas supply means, and a medium gas is blown from the gas blowing portion of the internal electrode into the plastic container to set a predetermined gas pressure in the exhaust pipe including the plastic container; and (d) a high frequency power source. A high-frequency power is supplied to the external electrode from the plasma to generate plasma around the internal electrode located in the plastic container, and the medium gas is dissociated by the plasma to coat a carbon film on the inner surface of the plastic container. A method for manufacturing an inner carbon film-coated plastic container, comprising: 7. An external electrode having a size that surrounds a container to be processed when the plastic container to be processed is inserted, and at least a mouth and a shoulder of the container when the plastic container to be processed is inserted. A spacer made of a dielectric material interposed between the external electrode and the external electrode; an exhaust pipe attached to the end surface of the external electrode on the side where the mouth of the container is located via an insulating member; An internal electrode inserted into the plastic container, a gas supply pipe having one end connected to the internal electrode and the other end extending to the exhaust pipe side and also serving as a power supply terminal, at least in the external electrode and An earth shield pipe, which is arranged on the outer periphery of the gas supply pipe portion located inside the exhaust pipe near the mouth of the container and is grounded; exhaust means attached to the exhaust pipe; A gas supply unit for supplying a medium gas to the gas supply pipe; a high-frequency power supply connected to the gas supply pipe; and a bias power supply connected to the external electrode. A device for forming a carbon film on the inner surface of a plastic container, wherein a gas blowing portion made of an insulating material for blowing a medium gas is provided in a portion located on the bottom side of the plastic container inserted into the external electrode. 8. When manufacturing an inner carbon film-covered plastic container using the carbon film forming apparatus according to claim 7, (a) a plastic container, which is an object to be treated, is formed in an outer electrode and a spacer made of a dielectric material. At least the outer periphery of the mouth and shoulder of the container is surrounded by the spacer, and the outer periphery of the other container part is surrounded by the external electrode; and (b) grounded. A gas supply pipe having an earth shield pipe arranged on the outer periphery is connected, and an internal electrode provided with a gas blowing portion made of an insulating material is provided on the end surface of the external electrode on the side where the mouth portion of the container is located via an insulating member. The exhaust pipe attached to the inside of the plastic container so that the gas blowing part is located on the bottom side of the container, and (c) exhausting gas inside and outside the container. After exhausting through the exhaust pipe by the pipe means, the medium gas is supplied from the gas supply pipe means to the internal electrode through the gas supply pipe, and the medium gas is blown into the plastic container from the gas blowing portion of the internal electrode. Setting a predetermined gas pressure in the exhaust pipe including the inside of the plastic container, and (d) applying a high frequency power from a bias power supply to the external electrode and passing a high high frequency power from a high frequency power supply through the gas supply pipe. Supplying the internal electrode, generating plasma in the plastic container, and dissociating the medium gas by the plasma to coat the carbon film on the inner surface of the plastic container. Manufacturing method of plastic container. 9. The gas blowing section is further provided in a side surface region near the inner electrode portion located on the bottom side of the plastic container inserted into the outer electrode. 7. A carbon film forming device on the inner surface of the plastic container according to any one of the above. 10. An external electrode having a size that surrounds a plastic container, which is an object to be processed, when the container is inserted, and an end face of the external electrode on a side where a mouth portion of the container is located via an insulating member. An attached exhaust pipe, an internal electrode inserted into the plastic container in the external electrode from the exhaust pipe side and provided with a gas blowing portion for blowing out a medium gas, and one end of which is connected to the internal electrode. A gas supply pipe having the other end extended to the exhaust pipe side and also serving as a power supply terminal, and a tip on the outer periphery of the gas supply pipe portion located at least in the external electrode and in the exhaust pipe near the mouth of the container Is placed with a desired gap from the internal electrodes,
A grounded earth shield tube, an insulating tube at least covered by the gas supply tube located in a gap region between the internal electrode and the tip of the earth shield tube, an exhaust unit attached to the exhaust tube, the gas An inner surface of a plastic container, comprising: a gas supply unit for supplying a medium gas to a supply pipe; a high-frequency power supply connected to the gas supply pipe; and a bias power supply connected to the external electrode. Carbon film forming equipment 11. In manufacturing an inner carbon film-coated plastic container using the carbon film forming apparatus according to claim 10, (a) a step of inserting the plastic container, which is the object to be treated, into an external electrode, b) A gas supply pipe having an insulating tube and a grounded earth shield pipe arranged on the outer periphery in this order is connected, and the internal electrode provided with a gas blowing portion is connected to the external electrode on the side where the mouth portion of the container is located. Inserting into the inside of the plastic container from an exhaust pipe attached to an end surface of the container via an insulating member, and (c) exhausting gas inside and outside the container through the exhaust pipe by an exhaust pipe means, and then supplying the gas supply pipe. A medium gas is supplied from the means to the internal electrode, and the medium gas is blown into the plastic container from the gas blowing portion of the internal electrode to move the inside of the plastic container. A step of setting a predetermined gas pressure in the exhaust pipe including: (d) applying a high-frequency power from a bias power supply to the external electrode, and supplying a high-frequency power from a high-frequency power supply to the internal electrode through the gas supply pipe A plasma is generated in the plastic container, and the medium gas is dissociated by the plasma to coat the carbon film on the inner surface of the plastic container. . 12. An external electrode having a size that surrounds a container to be processed when it is inserted, and at least a mouth and a shoulder of the container when the container to be processed is inserted. A spacer made of a dielectric material interposed between the external electrode and the external electrode; an exhaust pipe attached to the end surface of the external electrode on the side where the mouth of the container is located via an insulating member; An internal electrode that is inserted into the plastic container from the exhaust pipe side and is provided with a gas blowing portion for blowing out a medium gas; one end is connected to the internal electrode and the other end extends to the exhaust pipe side. Gas supply pipe also serving as a power supply terminal, and a tip inside the outer periphery of the gas supply pipe portion located at least in the external electrode and in the exhaust pipe near the mouth of the container Are spaced a desired gap To pole,
A grounded earth shield tube, an insulating tube at least covered by the gas supply tube located in a gap region between the internal electrode and the tip of the earth shield tube, an exhaust unit attached to the exhaust tube, the gas An inner surface of a plastic container, comprising: a gas supply unit for supplying a medium gas to a supply pipe; a high-frequency power supply connected to the gas supply pipe; and a bias power supply connected to the external electrode. Carbon film forming equipment 13. When manufacturing an inner carbon film-coated plastic container using the carbon film forming apparatus according to claim 12, (a) a plastic container, which is an object to be treated, is formed in an outer electrode and a spacer made of a dielectric material. At least the outer periphery of the mouth portion and the shoulder portion of the container is surrounded by the spacer, and the outer periphery of the other container portion is surrounded by the outer electrode; A gas supply pipe in which a grounded earth shield pipe is arranged in this order on the outer periphery is connected, and an internal electrode provided with a gas blowing portion is provided on the end surface of the external electrode on the side where the mouth portion of the container is located, with an insulating member. Inserting into the inside of the plastic container from an exhaust pipe attached via (c) exhausting gas inside and outside the container through the exhaust pipe by exhaust pipe means. After that, a medium gas is supplied from the gas supply pipe means to the internal electrode, and the medium gas is blown into the plastic container from the gas blowing portion of the internal electrode, so that the exhaust pipe including the inside of the plastic container has a predetermined gas pressure. And (d) applying high-frequency power from a bias power supply to the external electrode, and supplying high-frequency power from a high-frequency power supply to the internal electrode through the gas supply pipe to generate plasma in the plastic container. And dissociating the medium gas by this plasma to coat the carbon film on the inner surface of the plastic container.