JP2005226164A - Device for producing coating vessel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a device for forming a carbon film onto the inside face of a plastic vessel where the inside face of a plastic vessel can be coated with a carbon film with satisfactory film quality and uniform thickness. <P>SOLUTION: The device is provided with: an external electrode having a size, at the time when a plastic vessel as the object to be treated is inserted therein, to surround the outer circumference of the vessel; an exhaust tube fitted to the edge face of the external electrode on the side at which the mouth part of the vessel is located via an insulating member; an internal electrode inserted into the plastic vessel in the external electrode from the exhaust tube side and connected to the grounded side; an exhausting means fitted to the exhaust tube; a gas feeding means for feeding a medium gas to the internal electrode; and a high frequency power source connected to the external electrode. In the internal electrode, the part located in the bottom part side of the plastic vessel inserted into the external electrode is provided with a gas blowing-out part composed of an insulating material for blowing-out the medium gas. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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 surface carbon film-coated plastic container.

Plastic containers, such as PET bottles, have DLC (Diamond Like Car) on the inner surface to prevent the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water).
Attempts have been made to coat carbon films such as bon).

As a method for coating the carbon film on the inner surface of such a plastic container, Patent Document 1 (Japanese Patent Laid-Open No. 8-53116) and Patent Document 2 (Japanese Patent No. 2788412 (Japanese Patent Laid-Open No. 8-53117)) describe high frequency. A method using plasma is disclosed. Patent Document 3 (Japanese Patent Laid-Open No. 9-272567) discloses a method of coating a film with a carbon film using high-frequency plasma as an applied method. In Patent Document 4 (Japanese Patent No. 3072269 (Japanese Patent Laid-Open No. 10-226884)), a carbon film coating method corresponding to a specially shaped container is disclosed in Patent Document 5 (Japanese Patent No. 3115252 (Japanese Patent Laid-Open No. Hei 1).
No. 0-258825))) discloses a method for simultaneously coating a plurality of containers as a mass production technique. In addition, Non-Patent Document 1 (“K. Takemoto, et al, Proceedings of ADC / FC” discloses a technique for coating a carbon film on a plastic container.
T '99, p285 '', `` E. Shimamura et al, 10th years IAPRI World Conference 1997, p251
]).

Patent Document 2 (Patent No. 2788412 (JP-A-8-53117)), which is a basic invention for coating a carbon film on a plastic container using high-frequency plasma CVD
Will be described with reference to FIG. FIG. 12 is a cross-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, for example, a sealing plate 2 made of polytetrafluoroethylene on the frame 202.
03 is installed. The external electrode 201 has an inner shape that substantially conforms to the outer shape of a plastic container to be accommodated, for example, the bottle B. The outer electrode 201 preferably has an inner shape along the screw shape for the bottle cap at the base. The external electrode 201 includes a cylindrical main body 201a and a cap portion 201b attached to the upper end of the main body 201a, and also serves as a vacuum container. The gas exhaust pipe 204 includes the gantry 202 and the seal plate 2.
03 is communicated with the lower part of the external electrode 201.

The internal electrode 205 is inserted into the bottle B accommodated 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. A gas supply pipe 207 for supplying a CVD medium gas passes through the mount 202 and the seal plate 203 and communicates with the lower end of the internal electrode 205. The medium gas for CVD is supplied into the internal electrode 205 through the supply pipe 207 and supplied into the bottle B from the gas blowing hole 206.

The RF input terminal 208 is connected to the external electrode 2 through the mount 202 and the seal plate 203.
01 is connected to the bottom. The RF input terminal 208 is electrically insulated from the gantry 202. The lower end of the RF input terminal 208 is connected to the high frequency power supply 210 through the matching unit 209. The external electrode 201 is applied with high-frequency power for plasma generation from the high-frequency power source 210 through the matching unit 209 and the RF input terminal 208.

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

First, a plastic bottle B is inserted into the main body 201a of the external electrode 201, and the main body 201a
The bottle B is stored in the external electrode 201 in an airtight manner by attaching the cap 201b to the outer electrode 201. The gas in the external electrode 201 is exhausted through the gas exhaust pipe 204. At this time, the gas in the space inside and outside the bottle B accommodated in the external electrode 201 is exhausted through the opening of the seal plate 203. After reaching a prescribed degree of vacuum (representative value: 10 ⁻² to 10 ⁻⁵ Torr), a 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 out into the bottle B through the gas blowing hole 206. 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, for example, 2 × depending on the balance between the gas supply amount and the exhaust amount.
10 ⁻¹ to 1 × 10 ⁻² Torr is set. Thereafter, the high frequency power supply 210 to 50 to 1000
A high frequency power of W is applied 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, plasma is generated between the external electrode 201 and the internal electrode 205. At this time, since the plastic bottle B is stored in the external electrode 201 with almost no gap, plasma is generated in the plastic bottle B. The medium gas is dissociated or further ionized by the plasma to generate a film-forming species for forming a carbon film, and this film-forming species is deposited on the inner surface of the bottle B to form a carbon film. After the carbon film is formed to a predetermined thickness, the application of the high frequency power is stopped, the supply of the medium gas is stopped, the residual gas is exhausted, nitrogen, a rare gas, air, or the like is supplied into the external electrode 201, and this space Return inside to atmospheric pressure. Thereafter, the bottle B is removed from the external electrode 201. In this method, it takes 2-3 seconds to form a carbon film with a thickness of 30 nm.

JP-A-8-53116 Japanese Patent No. 2788412 (Japanese Patent Laid-Open No. 8-53117) JP 9-272567 A Japanese Patent No. 3072269 (Japanese Patent Laid-Open No. 10-226884) Japanese Patent No. 3115252 (Japanese Patent Laid-Open No. 10-258825) "K. Takemoto, et al, Proceedings of ADC / FCT '99, p285", "E. Shimamura et al, 10th years IAPRI World Conference 1997, p251"

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

The medium gas has a plurality of gas blowing holes 20 that are opened along the axial direction of the internal electrode 205.
6 is supplied into a plastic container (for example, bottle B) and exhausted from the mouth of the plastic container. For this reason, 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 larger conductance and promotes the gas flow from the gas blowing hole, The gas flow from the gas blowing hole near the bottom of the container far from the mouth is stagnant. As a result, the medium gas near the bottom of the container is exposed to the plasma for a longer time than the gas near the mouth of the container, so the molecules that are bound by the gas phase reaction may become too large and become powdery. is there.

In addition, depending on conditions such as gas flow rate, pressure, and electric field distribution at the gas outlet, a locally concentrated discharge may occur in and near the gas outlet. This causes problems such as non-uniformity, high-frequency power loss, and electrode temperature rise. In particular, the powdery substance is not coated as a thin film on the surface of the container, and becomes a foreign substance that accumulates thereon. The occurrence of such foreign matters 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 as in the case of using a carbon film does not occur.

  b). Powdery substances that can enter the beverage remain in the container.

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

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

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 be coated with a carbon film having a uniform thickness.

An object of this invention is to provide the manufacturing method of the plastic container by which the film | membrane quality was favorable and the carbon film which has a uniform film thickness was coated by 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.

An object of this invention is to provide the manufacturing method of the plastic container by which the carbon film with favorable film quality and uniform film thickness was coated on the inner surface at high speed.

The apparatus for forming a carbon film on the inner surface of a plastic container and the method for producing an inner surface carbon film-coated plastic container according to the present invention have the following configuration.

1) An external electrode having a size that surrounds the outer periphery of a plastic container, which is an object to be processed, and an end face of the external electrode on the side where the mouth of the container is located are attached via an insulating member An exhaust pipe, an internal electrode inserted into the plastic container in the external electrode from the exhaust pipe side and connected to the ground side, exhaust means attached to the exhaust pipe, and a medium in the internal electrode A gas supply means for supplying a gas; and a high-frequency power source connected to the external electrode, wherein the internal electrode is a medium gas at a portion located on a bottom side 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 blowing portion made of an insulating material for blowing out the gas is provided.

2) In manufacturing an inner surface carbon film-coated plastic container using the carbon film forming apparatus of 1), (a) a step of inserting a plastic container as an object to be processed into an external electrode;
) An internal electrode provided with a gas blowing portion made of an insulating material is connected to the inside of the plastic container from an exhaust pipe attached via an insulating member to an end face of the external electrode on the side where the mouth of the container is located. Inserting the gas blowing portion so as to be positioned on the bottom side of the container;
(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 to the internal electrode by the gas supply means, and the medium gas is supplied from the gas blowing portion of the internal electrode into the plastic container. And (d) supplying high-frequency power from a high-frequency power source to the external electrode and surrounding the internal electrode located in the plastic container. And a step of dissociating the medium gas with the plasma to coat the inner surface of the plastic container with a carbon film.

3) An external electrode having a size that surrounds a plastic container as an object to be processed and an end face of the external electrode on the side where the mouth of the container is located are attached via an insulating member. An exhaust pipe, an internal electrode inserted from the exhaust pipe side into the plastic container in the external electrode and connected to the ground side, exhaust means attached to the exhaust pipe, and medium gas to the internal electrode A plastic container comprising a gas supply means for supplying, a high-frequency power source connected to the internal electrode, and a bias power source connected to the external electrode, wherein the internal electrode is inserted into the external electrode An apparatus 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 out a medium gas is provided at a portion located on the bottom side of the plastic container.

4) In manufacturing an inner surface carbon film-coated plastic container using the carbon film forming apparatus of 3), (a) a step of inserting a plastic container as an object to be processed into an external electrode;
) An internal electrode provided with a gas blowing portion made of an insulating material is connected to the inside of the plastic container from an exhaust pipe attached via an insulating member to an end face of the external electrode on the side where the mouth of the container is located. Inserting the gas blowing portion so as to be positioned on the bottom side of the container;
(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 to the internal electrode by the gas supply means, and the medium gas is supplied from the gas blowing portion of the internal electrode into the plastic container. And (d) applying high frequency power from a bias power source to the external electrode, and applying high frequency power from a high frequency power source to the gas. Supplying the inner electrode through a supply pipe, generating plasma in the plastic container, dissociating the medium gas by the plasma, and coating the inner surface of the plastic container with a carbon film. A method for producing a carbon film-coated plastic container.

5) An external electrode having a size surrounding the plastic container as the object to be processed, and at least the mouth and shoulders of the container and the outside when the plastic container as the object to be processed is inserted. A spacer made of a dielectric material interposed between the electrodes, an exhaust pipe attached via an insulating member to an end face of the external electrode on the side where the mouth of the container is located, and the plastic in the external electrode An internal electrode inserted into the container from the exhaust pipe side and connected to the ground side; an exhaust means attached to the exhaust pipe; a gas supply means for supplying a medium gas to the internal electrode; and the external A high-frequency power source connected to the electrode, and the internal electrode is an insulating material for blowing a medium gas to a portion located on the bottom side of the plastic container inserted into the external electrode The gas blowout unit consisting of is provided a carbon film forming apparatus of the plastic container inner surface, wherein.

6) In manufacturing the inner surface carbon film-coated plastic container using the carbon film forming apparatus of 5), (a) at least the plastic container as the object to be processed is placed in the external electrode and in the spacer made of a dielectric material. The outer periphery of the mouth and shoulder of the container is surrounded by the spacer,
A step of inserting so that the outer periphery of the container portion other than this is surrounded by the external electrode;
) An internal electrode provided with a gas blowing portion made of an insulating material is connected to the inside of the plastic container from an exhaust pipe attached via an insulating member to an end face of the external electrode on the side where the mouth of the container is located. Inserting the gas blowing portion so as to be positioned on the bottom side of the container;
(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 to the internal electrode by the gas supply means, and the medium gas is supplied from the gas blowing portion of the internal electrode into the plastic container. And (d) supplying high-frequency power from a high-frequency power source to the external electrode and surrounding the internal electrode located in the plastic container. And a step of dissociating the medium gas with the plasma to coat the inner surface of the plastic container with a carbon film.

7) An external electrode having a size surrounding the container when the plastic container as the object to be processed is inserted, and at least the mouth and shoulders of the container and the outside when the plastic container as the object to be processed is inserted. A spacer made of a dielectric material interposed between the electrodes, an exhaust pipe attached via an insulating member to an end face of the external electrode on the side where the mouth of the container is located, and the plastic in the external electrode An internal electrode inserted into the container; a gas supply pipe having one end connected to the internal electrode and the other end serving as a power supply terminal extending toward the exhaust pipe; and at least the external electrode and the opening of the container An earth shield pipe disposed on the outer periphery of the gas supply pipe portion located in the exhaust pipe near the portion, grounded, exhaust means attached to the exhaust pipe, and the gas supply pipe A gas supply means for supplying a quality gas; a high-frequency power source connected to the gas supply pipe; and a bias power source connected to the external electrode. The internal electrode is 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 blowing portion made of an insulating material for blowing out a medium gas is provided at a portion located on the bottom side of the plastic container.

8) In manufacturing the inner surface carbon film-coated plastic container using the carbon film forming apparatus of 7), (a) the plastic container as the object to be processed is placed at least in the outer electrode and in the spacer made of a dielectric material. The outer periphery of the mouth and shoulder of the container is surrounded by the spacer,
A step of inserting so that the outer periphery of the container portion other than this is surrounded by the external electrode;
) A gas supply pipe having a grounded 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 connected to the end face of the external electrode on the side where the mouth of the container is located A step of inserting from the exhaust pipe attached via an insulating member into the plastic container so that the gas blowing portion is located on the bottom side of the container; and (c) exhaust gas inside and outside the container by exhaust pipe means After exhausting through the exhaust pipe, 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. A step of setting the inside of the exhaust pipe including the inside to a predetermined gas pressure, and (d) applying high frequency power from a bias power source to the external electrode, Supplying high frequency power from a frequency power source to the internal electrode through the gas supply pipe, generating plasma in the plastic container, dissociating the medium gas by the plasma, and coating a carbon film on the inner surface of the plastic container A method for producing an inner surface carbon film-covered plastic container.

9) An external electrode having a size that surrounds the plastic container that is the object to be processed and an end face of the external electrode on the side where the mouth of the container is located are attached via an insulating member. An exhaust pipe, an internal electrode inserted from the exhaust pipe side into the plastic container in the external electrode and provided with a gas blowing part for blowing out a medium gas, one end connected to the internal electrode, and the other end A gas supply pipe also serving as a power supply terminal extended to the exhaust pipe side, and at least a tip of the inner end of the gas supply pipe portion located in the exhaust pipe located at least in the external electrode and in the vicinity of the mouth of the container At least in the gas supply pipe located in the gap region between the electrode and the ground shield pipe which is arranged with a desired gap and is grounded, and the inner electrode and the tip of the earth shield pipe A coated insulating tube; 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 source connected to the gas supply pipe; An apparatus for forming a carbon film on the inner surface of a plastic container, comprising: a bias power source connected to an electrode.

10) In manufacturing an inner surface carbon film-coated plastic container using the carbon film forming apparatus of 9), (a) a step of inserting a plastic container as an object to be processed 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 an internal electrode provided with a gas blowing part is connected to the external electrode on the side where the mouth of the container is located Inserting into the inside of the plastic container from an exhaust pipe attached to the end surface of the gas supply pipe via an insulating member; and (c) exhausting the gas inside and outside the container through the exhaust pipe by an exhaust pipe means, Supplying a medium gas from the means to the internal electrode, blowing the medium gas into the plastic container from a gas blowing portion of the internal electrode, and setting the inside of the exhaust pipe including the inside of the plastic container to a predetermined gas pressure; d) applying high frequency power from a bias power source to the external electrode, and applying high frequency power from a high frequency power source to the internal electrode through the gas supply pipe. And supplying a carbon film to the plastic container, and dissociating the medium gas by the plasma to coat a carbon film on the inner surface of the plastic container. Production method.

11) An external electrode having a size that surrounds the plastic container as the object to be processed, and at least the mouth and shoulder of the container when the plastic container as the object to be processed is inserted A spacer made of a dielectric material interposed between the electrodes, an exhaust pipe attached via an insulating member to an end face of the external electrode on the side where the mouth of the container is located, and the plastic in the external electrode An internal electrode inserted into the container from the exhaust pipe side and provided with a gas blowing part for blowing out a medium gas, and one end connected to the internal electrode and the other end extended to the exhaust pipe side A gas supply pipe also serving as a terminal, and at least a distal end of the gas supply pipe portion located in the outer pipe and in the exhaust pipe near the mouth of the container, the inner electrode and a desired An earth shield pipe which is arranged with a gap and is grounded, an insulating tube which is at least covered with the gas supply pipe located in a gap region between the internal electrode and the tip of the earth shield pipe, and is attached to the exhaust pipe A gas supply means for supplying a medium gas to the gas supply pipe, a high-frequency power source connected to the gas supply pipe, and a bias power supply connected to the external electrode. An apparatus for forming a carbon film on the inner surface of a plastic container.

12) In manufacturing the inner surface carbon film-coated plastic container using the carbon film forming apparatus of 11), (a) the plastic container as the object to be processed is placed at least in the outer electrode and in the spacer made of a dielectric material. Inserting the outer periphery of the mouth and shoulders of the container so that the outer periphery of the container is surrounded by the spacer, and the outer periphery of the container part other than that is surrounded by the 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 an internal electrode provided with a gas blowing portion is connected to the external side on the side where the mouth of the container is located. A step of inserting into the inside of the plastic container from an exhaust pipe attached to the end face of the electrode via an insulating member; and (c) supplying the gas after exhausting the gas inside and outside the container through the exhaust pipe by an exhaust pipe means Supplying medium gas from the pipe means to the internal electrode, blowing the medium gas into the plastic container from the gas blowing part of the internal electrode, and setting the inside of the exhaust pipe including the inside of the plastic container to a predetermined gas pressure; (D) applying high-frequency power from a bias power source to the external electrode, and supplying high-frequency power from a high-frequency power source to the internal electrode with the gas supply pipe An inner surface carbon film-covered plastic container comprising the steps of: generating a 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. Manufacturing method.

ADVANTAGE OF THE INVENTION According to this invention, the carbon film formation apparatus to the inner surface of the plastic container which can coat the carbon film with favorable film quality on the inner surface of the plastic container and further uniform thickness can be provided.

In addition, according to the present invention, it is possible to provide a method capable of producing a plastic container having a good film quality and having a uniform film thickness coated on the inner surface and having an excellent barrier property against oxygen and carbon dioxide.

Furthermore, according to the present invention, it is possible 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.

Furthermore, according to the present invention, there is provided a method capable of mass-producing a plastic container having a good film quality, a carbon film having a uniform film thickness coated on the inner surface at a high speed, and having an excellent barrier property against oxygen and carbon dioxide. Can be provided.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

(First embodiment)
FIG. 1 is a cross-sectional view showing an apparatus for forming a carbon film on the inner surface of a plastic container according to the first embodiment.
FIG. 2 is an enlarged cross-sectional view showing the internal electrode of FIG.
A cylindrical support member 2 having flanges 1 a and 1 b at the upper and lower ends is placed on an annular base 3. A cylindrical metal external electrode body 4 is disposed in the support member 2. A disk-shaped metal external electrode bottom member 5 is detachably attached to the bottom of the external electrode 4. The external electrode main body 4 and the external electrode bottom member 5 constitute a bottomed cylindrical external electrode 6 having a space of a size capable of installing a plastic container (for example, a plastic bottle) B that forms a carbon film. The disk-shaped insulator 7 is disposed 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 main body 4 by a pusher (not shown) to open and close the bottom of the external electrode main body 4. To do.

The annular insulating member 8 is placed on the upper surface of the external electrode 6 so that the upper surface of the annular insulating member 8 is flush with the upper flange 1 a of the cylindrical support member 2. The gas exhaust pipe 10 having upper and lower flanges 9a and 9b includes an upper flange 1a of the support member 2 and the annular insulating member 8.
It is mounted 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 screws (not shown) from the lower flange 9 b of the exhaust pipe 10 to the upper flange 1 a of the support member 2. Further, by screwing a screw (not shown) from the lower flange 9b of the exhaust pipe 10 through the annular insulating portion 8 to the main body 4 of the external electrode 6, the exhaust pipe 10 is connected 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 and the annular insulating member 8 and the external electrode 6 are fixed in a mounting structure in which the exhaust pipe 10 and the external electrode 6 are not electrically connected by screws. 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. The lid 12 is attached to the upper flange 9 a of the exhaust pipe 10.

For example, the high frequency power supply 13 that outputs high frequency power with a frequency of 13.56 MHz is connected to the cable 1.
4 and the power supply terminal 15 are connected to the main body 4 of the external electrode 6. The matching unit 16 is interposed in the cable 15 between the high-frequency power source 13 and the power supply terminal 15.

The gas supply pipe 17 passes through the lid 12 and is inserted through the gas exhaust pipe 10 into a portion corresponding to the mouth of the plastic bottle B in the main body 4 of the external electrode 6. A substantially cylindrical metal internal electrode 18 is disposed in the vicinity of the bottom of the plastic 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 is a gas blowing portion made of an insulating material for blowing a medium gas to the bottom portion with a gas flow path 19 cut out in the central axis, for example, plastic or ceramic. A gas blowing tube 20 made of such an insulating material is inserted.

  The diameter of the internal electrode 18 is equal to or smaller than the diameter of the cap of the bottle B.

The internal electrode 18 is 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. For this reason, it is preferable that the surface of the internal electrode 18 is previously sandblasted to increase the surface roughness and make it difficult to peel off the carbon film deposited on the surface. However, the method of smoothing the surface also has the advantage that the carbon film deposited can be easily peeled off by making it very smooth, and if it does not remain on the internal electrode, the internal electrode cleaning becomes unnecessary.

Next, a method for producing an inner surface carbon film-coated plastic container will be described using the carbon film forming apparatus shown in FIG.

The external electrode bottom member 5, the disk-like insulator 7 and the base 3 are removed by a pusher (not shown) to open the bottom of the external electrode body 4. Subsequently, after inserting a plastic container, for example, a plastic bottle B from the bottom side of the external electrode body 4 opened from the mouth side of the bottle B, the external electrode bottom member 5 is placed on 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 plastic bottle B is placed in the internal space of the external electrode 6 composed of the external electrode main 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, gas inside and outside the exhaust pipe 19 and the PET 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 blown into the plastic bottle B from the gas blowing pipe 20 made of an insulating material inserted into the bottom of the internal electrode 18. This medium gas further flows toward the mouth of the plastic bottle B. Subsequently, 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, for example, high frequency power having a frequency of 13.56 MHz is supplied from the high frequency power supply 13 to the cable 1.
4. Supply to the main body 4 of the external electrode 6 through the matching unit 16 and the power supply terminal 15. At this time, plasma is generated around the internal electrode 18. Due to the generation of the 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 with a uniform thickness.

After the thickness of the carbon film reaches a predetermined film thickness, the supply of the high frequency power from the high frequency power supply 13 is stopped, the supply of the medium gas is stopped, the residual gas is exhausted, and the exhaust of the gas is stopped. , Nitrogen, rare gas, air, or the like is supplied into the plastic bottle B through the gas supply pipe 17 through the gas flow path 19 and the gas blowing pipe 20 of the internal electrode 18, and the inside and outside of the plastic bottle B is returned to the atmospheric pressure. Remove the carbon film-coated PET bottle. Thereafter, the plastic bottle B is exchanged according to the above-described order, and the next plastic bottle coating operation is started.

The medium gas is basically hydrocarbon, for example, alkanes such as methane, ethane, propane, butane, pentane and hexane; alkenes such as ethylene, propylene, butene, pentene and butadiene; alkynes such as acetylene; benzene, Aromatic hydrocarbons such as toluene, xylene, 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; methyl Nitrogen-containing hydrocarbons such as amine, ethylamine and aniline can be used, and other carbon monoxide and carbon dioxide can also be used. Ar and He are also used to stabilize plasma and optimize plasma characteristics.
In some cases, a rare gas such as the above is mixed with the medium gas.

The high frequency power is generally 13.56 MHz and 100 to 1000 W, but is not limited thereto. Moreover, the application of these electric powers may be continuous or intermittent (pulsed).

As described above, according to the first embodiment, by supplying the medium gas from the bottom of the internal electrode 18 into the plastic bottle B, a gas flow from the bottom of the plastic bottle B toward the mouth can be forcibly generated. . For this reason, it can prevent that the residence part of gas is made in the PET bottle B. As a result, it is possible to coat the inner surface of the plastic bottle B with a carbon film having good film quality with little contamination and having a uniform film thickness.

Further, a gas blowing tube 20 made of an insulating material in which a medium gas is inserted into the bottom of the internal electrode 18.
By blowing out from the plasma, it is possible to prevent the plasma from locally concentrating inside or near the gas blowing holes.

That is, providing the gas blowing portion at the bottom of the internal electrode can exert the above-described effects, but on the other hand, depending on the plasma generation conditions such as the supply amount of the medium gas and the pressure in the PET bottle B, the bottom of the metal internal electrode is provided. If the gas blowing hole is directly opened as the gas blowing portion, there is a possibility that plasma is locally generated in or near the gas blowing hole. When plasma is generated locally in the vicinity of the gas blowing hole at the bottom of the internal electrode in this way, the plasma density at that location increases, so that a large amount of powder is generated, and contamination (powder) is generated on the inner surface of the plastic bottle B. Mixing or non-uniform film thickness.

For this reason, as shown in FIG. 2, by inserting a gas blowing pipe 20 made of an insulating material at the bottom of the internal electrode 18, and blowing out the medium gas from the gas blowing pipe 20,
The concentration of plasma generated in the PET bottle B can be made uniform by preventing local concentration of plasma in the vicinity of the gas blowing tube 20. As a result, it is possible to coat the inner surface of the PET bottle B with a carbon film having a good film quality with little powder mixing and a uniform film thickness.

Therefore, according to the first embodiment, it is possible to manufacture an inner surface carbon film-coated PET bottle with excellent barrier properties that prevents permeation of oxygen from outside and permeation of carbon dioxide from the inside (for example, carbonated drinking water). .

(Example 1)
As the internal electrode 18, one having a structure in which a gas blowing tube 20 having an inner diameter of 1 mm made of polytetrafluoroethylene was inserted into the bottom of a stainless steel sealed tube having an outer diameter of 16 mm and a length of 70 mm shown in FIGS. 1 and 2 was used. .

This internal electrode 18 is inserted into a plastic bottle B accommodated in the external electrode 6 shown in FIG. 1, and C ₂ H ₂ gas as a medium, a gas flow rate of 20 sccm, a gas pressure in the plastic bottle B and the exhaust pipe 10 are set. The inner surface of the PET bottle B was coated with a carbon film under the conditions of 0.1 Torr and a high frequency supplied from a high frequency power source at 13.56 MHz.

(Comparative Example 1)
As an internal electrode, 1 is attached to the bottom of a stainless cantilever tube with an outer diameter of 16 mm and a length of 70 mm
A carbon film was coated on the inner surface of the plastic bottle B by the same method as in Example 1 except that a gas blowing hole having a hole diameter of 1 mm was used.

As a result, in Example 1, the carbon film could be coated on the inner surface of the plastic bottle B. On the other hand, 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. The formation of this black powder film is thought to be due to the fact that high density plasma was locally generated in and near the gas blowing holes.

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

(Second Embodiment)
FIG. 4 is a cross-sectional view showing a carbon film forming apparatus on the inner surface of a plastic container according to the second embodiment. 4 that are the same as those in FIG. 1 referred to in the first embodiment described above are denoted by the same reference numerals and description thereof is omitted.

In this carbon film forming apparatus, a bias power source 23 is connected to the external electrode body 4 of the external electrode 6 through a cable 24 and a power supply terminal 25. The matching unit 26 includes the bias power source 2.
3 and the cable 24 between the power supply terminals 25.

The lid 12 that has an insulating ring 26 at the center and is grounded is hermetically fixed to the upper flange 9 a of the gas exhaust pipe 10. The casing 27 is attached on the lid body 12.

A gas supply pipe 17 having an internal electrode 18 detachably attached to 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 casing 27, and the gas exhaust pipe 10.
And inserted into the body 4 of the external electrode 6 (in the portion corresponding to the central portion of the plastic bottle B to be inserted). The upper end of the gas supply pipe 17 is connected to the lower end of a gas introduction pipe 28 inserted through the housing 27 from the outside 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 the central axis and a gas blowing portion made of an insulating material for blowing out a medium gas at the bottom, for example, plastic, A gas blowing tube 20 made of an insulating material such as ceramic is inserted.

The flange pipe 30 and the earth shield pipe 31 connected to the lower end of the flange pipe 30 are:
The gas exhaust pipe 10 and the external electrode 6 are arranged so as to cover the portion of the gas supply pipe 17 located in the portion corresponding to the central part of the plastic bottle B in the main body 4. In addition,
The earth shield pipe 31 is located from the gas exhaust pipe 10 in the vicinity of the mouth of the plastic bottle B to a location corresponding to the central part of the plastic bottle B. The upper end of the flange tube 30 is connected to the back surface of the lid body 12. That is, the earth shield pipe 31 is connected to the lid body 12 grounded through the flange pipe 30.

The high-frequency power supply 32 is connected to the side surface of the gas supply pipe 17 that also serves as a terminal for high-frequency power through a cable 33 and a power supply terminal 34. The matching unit 35 includes the high-frequency power source 3.
2 and the cable 33 between the power supply terminal 34.

Next, a method for producing an inner surface carbon film-coated plastic container will be described using the carbon film forming apparatus shown in FIG.

The external electrode bottom member 5, the disk-like insulator 7 and the base 3 are removed by a pusher (not shown) to open the bottom of the external electrode body 4. Subsequently, after inserting a plastic container, for example, a plastic bottle B from the bottom side of the external electrode body 4 opened from the mouth side of the bottle B, the external electrode bottom member 5 is placed on 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 plastic bottle B is placed in the internal space of the external electrode 6 composed of 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, gas inside and outside the exhaust pipe 10 and the PET 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 inserted into the bottom of the internal electrode 18. Blow in. This medium gas further flows toward the mouth of the plastic bottle B. Subsequently, 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 unit 26 and the power supply terminal 25. Thereafter, or simultaneously, high-frequency power is supplied from the high-frequency power source 32 to the gas supply pipe 17 through the cable 33, the matching unit 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 electrode 18. Further, since the exhaust pipe 10 located above the external electrode 6 is grounded, the bias voltage is directed from the external electrode 6 toward the internal electrode 18 with the exhaust pipe 10 as a reference potential, that is, to the generated plasma. Can be applied.

As a result, a) When using high-frequency power, a high electron density is obtained compared to high-frequency power, particularly under low gas pressure conditions, so that the collision frequency with the medium gas is increased and the film-forming seed density can be increased.
b) Since the potential difference from the plasma potential can be varied by adjusting the bias power, the ion energy incident on the inner surface of the PET bottle B can be adjusted. c) Since the ion density is proportional to the electron density, it is used in combination with the above potential difference adjustment. By doing so, the ion flux incident on the inner surface of the plastic bottle B can be controlled. Bias power was applied to the film-forming 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 thickness, the bias power source 23 and the high-frequency power source 3
2 stops supply of bias power and high-frequency power, stops supply of medium gas, exhausts residual gas, stops exhausting gas, and then supplies nitrogen, rare gas, air or the like to the gas introduction pipe 2
8 is supplied into the PET bottle B through the gas supply pipe 17 through the gas flow path 19 and the gas blowing pipe 20 of the internal electrode 18, the inside and outside of the PET bottle B are returned to atmospheric pressure, and the inner surface carbon film coated PET bottle is taken out. Then, replace 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 first embodiment can be used.

The high-frequency power is generally defined as 30 to 300 MHz, but is not limited thereto. Moreover, the application of these electric powers may be continuous or intermittent (pulsed).

The bias power is generally 13.56 MHz and 100 to 1000 W, but is not limited thereto. Also, this bias power application can be continuous or intermittent (
It may be pulsed).

As described above, according to the second embodiment, by supplying the medium gas from the bottom of the internal electrode 18 into the plastic bottle B, the gas flow from the bottom of the plastic bottle B toward the mouth can be forcibly generated. it can. For this reason, it can prevent that the residence part of gas is made in the PET bottle B. As a result, it is possible to coat the inner surface of the plastic bottle B with a carbon film having good film quality with little contamination and having a uniform film thickness.

Further, a gas blowing tube 20 made of an insulating material in which a medium gas is inserted into the bottom of the internal electrode 18.
By blowing out the air, the concentration of the plasma generated in the PET bottle B can be made uniform by preventing the concentration of discharge in the vicinity of the gas blowing tube 20 as in the first embodiment. As a result, it is possible to coat the inner surface of the PET bottle B with a carbon film having a good film quality with little powder mixing and a uniform film thickness.

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

Therefore, an inner surface carbon film-coated PET bottle with excellent barrier properties that prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water) can be produced more mass-produced.

Similarly, unnecessary plasma is generated between the gas supply pipe 17 to which high-frequency power is applied and the grounded exhaust pipe 10 (that is, in the exhaust pipe 10), and the coating efficiency of the carbon film is lowered. For this reason, the earth shield pipe 31 is disposed on the outer periphery of the gas supply pipe 17 so as to be positioned in the gas exhaust pipe 10 in the vicinity of the mouth of the plastic bottle B, and this earth shield pipe 3
1 is grounded through a flange pipe 30 that supports it, and even if high-frequency power is supplied to the gas supply pipe 17 penetrating the inside of the earth shield pipe 31, the inside of the exhaust pipe 10 that is the exhaust path of the medium gas Therefore, generation of unnecessary plasma can be prevented. As a result, it is possible to prevent consumption of high-frequency power accompanying unnecessary plasma generation.
The regular plasma generation efficiency can be increased, and the coating speed of the carbon film can be improved.

(Example 2)
As the internal electrode 18, one having a structure in which a gas blowing tube 20 having an inner diameter of 1 mm made of polytetrafluoroethylene was inserted into the bottom of a stainless steel sealed tube having an outer diameter of 16 mm and a length of 70 mm shown in FIGS. 1 and 2 was used. .

This internal electrode 18 is inserted into a plastic bottle B accommodated in the external electrode 6 shown in FIG. 4, and C ₂ H ₂ gas as a medium, a gas flow rate of 20 sccm, a gas pressure in the plastic bottle B and the exhaust pipe 10 are set. A carbon film was coated on the inner surface of the PET bottle B under the conditions of 0.1 Torr, a high frequency supplied from a high frequency power supply of 100 MHz, and a bias high frequency from a bias power supply of 13 MHz.

(Comparative Example 2)
As an internal electrode, 1 is attached to the bottom of a stainless cantilever tube with an outer diameter of 16 mm and a length of 70 mm.
A carbon film was coated on the inner surface of the plastic bottle B in the same manner as in Example 2 except that a gas blowing hole having a hole diameter of 1 mm was used.

As a result, in Example 2, the carbon film could be coated on the inner surface of the plastic bottle B at a high speed.
In contrast, in Comparative Example 2, a black powder film was formed on the inner surface of the bottom of the PET bottle B. The formation of this black powder film is thought to be due to the fact that locally high-density plasma was generated due to the concentration of discharge in the vicinity of the gas blowing holes.

In the second embodiment, the gas blowing portion made of the insulating material is constituted by the gas blowing tube 20 made of the insulating material shown in FIG. 5. However, the present invention is not limited to this, and for example, a gas made of the insulating material as shown in FIG. The blow-out portion is composed of a cap 22 made of an insulating material such as plastic or ceramic in which a gas blow-out hole 21 is opened in the central axis direction. You may attach to a bottom part so that the said gas flow path 19 may be connected. In the configuration shown in FIG. 6, the cap 22
You may open a gas blowing hole in the side wall.

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

A cylindrical support member 42 having flanges 41 a and 41 b at the upper and lower ends is placed on an annular base 43. A cylindrical metal external electrode body 44 is disposed in the support member 42. A disk-shaped metal external electrode bottom member 45 is detachably attached to the bottom of the external electrode 44. The external electrode main body 44 and the external electrode bottom member 45 constitute a bottomed cylindrical external electrode 46 having a space of a size capable of installing a plastic container (for example, a plastic bottle) B that forms a carbon film. A disk-shaped insulator 47 is disposed 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 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.

A cylindrical spacer 49 made of a dielectric material having a cavity 48 formed by combining a cylinder and a truncated cone corresponding to the mouth and shoulder of the plastic bottle B inserted therein is the main body of the external electrode 46. 44 is inserted in the upper part. 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. By inserting and fixing the columnar spacer 49 to the upper part of the main body 44 in the external electrode 46 in this way, when the plastic bottle B is inserted from the bottom side of the external electrode main body 44, the mouth and shoulder of the plastic bottle B are inserted. The portion is accommodated in the cavity 48 of the spacer 49, and the other plastic bottle B portion is accommodated in the external electrode 46.

Examples of the dielectric material constituting the spacer 49 include plastic or ceramic. Various plastics can be used,
In particular, a fluororesin such as polytetrafluoroethylene having a low high-frequency loss and excellent heat resistance is preferable. As the ceramic, alumina, steatite with low high-frequency loss, or Macor with high machinability is preferable.

The annular insulating member 50 is placed on the upper surface of the external electrode 46 so that the upper surface of the annular insulating member 50 is flush with the upper flange 41 a of the cylindrical support member 42. Up and down flange 5
A gas exhaust pipe 52 having 1 a and 51 b is placed 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 screws (not shown) from the lower flange 51 b of the exhaust pipe 52 to the upper flange 41 a of the support member 42. Further, a screw (not shown) is connected to the annular insulating portion 50 from the lower flange 51b of the exhaust pipe 52.
And the exhaust pipe 52 is fixed to the annular insulating member 50 and the external electrode 46, and the annular insulating member 50 is fixed to the external electrode 46. Is also fixed. The exhaust pipe 52 and the annular insulating member 50 and the external electrode 46 are fixed to each other by a mounting structure in which the exhaust pipe 52 and the external electrode 46 are not electrically connected by screws. 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. The lid 54 is attached to the upper flange 51a of the exhaust pipe 52.

For example, the high frequency power supply 55 that outputs high frequency power with a frequency of 13.56 MHz is the cable 5
6 and the power supply terminal 57 are connected to the main body 44 of the external electrode 46. Matching unit 5
8 is interposed in the cable 56 between the high-frequency power source 55 and the power supply terminal 57.

A gas supply pipe 59 passes through the lid 54 and passes through the gas exhaust pipe 52 to form the external electrode 46.
The main body 44 is inserted into a portion corresponding to the mouth of the plastic bottle B. A substantially cylindrical metal internal electrode 60 is disposed in the vicinity of the bottom of the plastic bottle B inserted into the external electrode 46, and its upper end is detachably attached to the lower end of the gas supply pipe 59. . The internal electrode 60 has a gas passage 61 made of an insulating material such as plastic or ceramic, which is a gas blowing portion made of an insulating material for blowing out a medium gas at the bottom, with a gas channel 61 cut out in the central axis. A tube 62 is inserted.

  The diameter of the internal electrode 60 is equal to or smaller than the diameter of the cap of the bottle B.

The internal electrode 60 is made of a heat-resistant metal material such as tungsten or stainless steel, but may be made of aluminum. Further, 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. For this reason, it is preferable that the surface of the internal electrode 60 be previously sandblasted to increase the surface roughness and make it difficult to peel off the carbon film deposited on the surface.

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

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

Next, the gas inside and outside 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 61 of the internal electrode 60 through the gas supply pipe 59 and blown out into the plastic bottle B from the gas blowing pipe 62 made of an insulating material inserted into the bottom of the internal electrode 60. This medium gas further flows toward the mouth of the plastic bottle B. Subsequently, 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, for example, high-frequency power having a frequency of 13.56 MHz is supplied from the high-frequency power supply 55 to the cable 5.
6. Supply to the main body 44 of the external electrode 46 through the matching unit 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 a uniform carbon film having a uniform thickness is coated on the inner surfaces of the external electrode 46 and the PET bottle B in the spacer 49.

After the thickness of the carbon film reaches a predetermined thickness, the supply of the high frequency power from the high frequency power supply 55 is stopped, the supply of the medium gas is stopped, the residual gas is exhausted, and the exhaust of the gas is stopped. , Nitrogen, rare gas, air, or the like is supplied into the plastic bottle B through the gas supply pipe 59 through the gas flow path 61 and the gas blowing pipe 62 of the internal electrode 60, and the inside and outside of the plastic bottle B is returned to the atmospheric pressure. Remove the carbon film-coated PET bottle. Thereafter, the plastic bottle B is exchanged according to the above-described order, and the next plastic 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 13.56 MHz and 100 to 1000 W, but is not limited thereto.

As described above, according to the third embodiment, by supplying the medium gas from the bottom of the internal electrode 60 into the plastic bottle B, the gas flow from the bottom of the plastic bottle B toward the mouth can be forcibly generated. it can. For this reason, it can prevent that the residence part of gas is made in the PET bottle B. As a result, it is possible to coat the inner surface of the plastic bottle B with a carbon film having good film quality with little contamination and having a uniform film thickness.

Further, a gas blowing pipe 62 made of an insulating material with a medium gas inserted into the bottom of the internal electrode 60.
By blowing out the air, the concentration of the plasma in the vicinity of the gas blowing tube 62 can be prevented and the density of the plasma generated in the plastic bottle B can be made uniform as in the first embodiment. As a result, it is possible to coat the inner surface of the PET bottle B with a carbon film having a good film quality with little powder mixing and a uniform film thickness.

Further, by inserting and fixing a cylindrical spacer 49 made of a dielectric material having a cavity 48 on the top of the external electrode 46, not only the inner surface of the plastic bottle B from the shoulder to the bottom side in the generation of the plasma. A carbon film having a uniform thickness can be coated on the inner surface of the shoulder portion from the mouth portion of the plastic bottle B facing the spacer 49 made of the dielectric material.

Therefore, the inner surface carbon film-coated PET bottle having excellent barrier properties that prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water) can be mass-produced.

In addition, the shape of the member covering the mouth portion and the shoulder portion of the plastic bottle B is complicated, but by forming the spacer 49 corresponding to these members with a dielectric material such as plastic capable of injection molding, Compared to the conventional case where all the members including these members are constituted by external electrodes, it can be manufactured easily. Furthermore, the entire apparatus can be reduced in weight as compared with the case where all of these members including the external electrodes are made of a conductive material such as metal as in the prior art.

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

In the third embodiment, the gas blowing portion made of the insulating material is constituted by the gas blowing tube 62 made of the insulating material shown in FIG. 7, but not limited thereto, for example, the above-described FIGS.
The gas blowout part made of an insulating material is composed of a cap made of an insulating material such as plastic or ceramic in which a gas blowout hole is opened in the central axis direction. It may be attached to the bottom of the internal electrode so as to communicate with the gas flow path. In such a configuration, a gas blowing hole may be opened in the side wall of the cap.

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

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

In this carbon film forming apparatus, a bias power source 63 is connected to the external electrode body 44 of the external electrode 46 through a cable 64 and a power supply terminal 65. The matching unit 66 is interposed in the cable 64 between the bias power source 63 and the power supply terminal 65.

The lid 54 that has an insulating ring 67 at the center and is grounded is hermetically fixed to the upper flange 51 a of the gas exhaust pipe 52. The casing 68 is attached on the lid 54.

The gas supply pipe 59 also serves as a terminal for high-frequency power, penetrates the insulating ring 67 of the lid 54 from the inside of the casing 68, passes through the gas exhaust pipe 52, and the spacer 49 in the external electrode 46.
Has been inserted inside. The upper end of the gas supply pipe 59 is connected to the lower end of a gas introduction pipe 69 inserted through the housing 68 from the outside via an insulating joint 70.

The flange pipe 71 and the earth shield pipe 72 connected to the lower end of the flange pipe 71 are:
The gas exhaust pipe 52 and the gas supply pipe 59 located in the spacer 49 are disposed so as to cover them. The earth shield pipe 72 is located in the spacer 49 and in the gas exhaust pipe 52 in the vicinity of the spacer 49. The upper end of the flange tube 71 is connected to the back surface of the lid 54. That is, the earth shield pipe 72 is connected to the lid 54 grounded through the flange pipe 71.

The high-frequency power source 73 is connected to the side surface of the gas supply pipe 59 that also serves as a terminal for high-frequency power through a cable 74 and a power supply terminal 75. The matching unit 76 is provided with the high-frequency power source 7.
3 and the cable 74 between the power supply terminals 75.

Next, a method for producing an inner surface carbon film-coated plastic container will be described using the carbon film forming apparatus shown in FIG.

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

Next, the gas inside and outside 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 PET bottle B is supplied from the gas blowing pipe 62 made of an insulating material inserted into the bottom of the internal electrode 61. Blow in. This medium gas further flows toward the mouth of the plastic bottle B. Subsequently, 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 simultaneously, high-frequency power is supplied from the high-frequency power source 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. The earth shield pipe 72 is disposed on the outer periphery of the gas supply pipe 59 so as to be located in the spacer 49 and in the gas exhaust pipe 52 in the vicinity of the spacer 49 and is grounded through the flange pipe 71. Using the earth shield tube 72 as a reference potential, a bias voltage can be applied from the external electrode 46 toward the internal electrode 60, that is, toward the generated plasma.

As a result, a) When using high-frequency power, a high electron density is obtained compared to high-frequency power, particularly under low gas pressure conditions, so that the collision frequency with the medium gas is increased and the film-forming seed density can be increased.
b) Since the potential difference from the plasma potential can be varied by adjusting the bias power, the ion energy incident on the inner surface of the PET bottle B can be adjusted. c) Since the ion density is proportional to the electron density, it is used in combination with the above potential difference adjustment. By doing so, the ion flux incident on the inner surface of the plastic bottle B can be controlled. Bias power is applied to the film-forming species obtained 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 46 by applying the bias voltage to the internal electrode 60. A uniform carbon film having a uniform thickness can be coated on the inner surface of the PET bottle B in the external electrode 46 at a high speed.

After the carbon film reaches a predetermined thickness, the bias power source 63 and the high-frequency power source 7
3, the supply of bias power and high-frequency power from 3 is stopped, the supply of medium gas is stopped, the residual gas is exhausted, the exhaust of gas is stopped, and then nitrogen, rare gas, air, or the like is supplied to the gas introduction pipe 6
9 through the gas supply pipe 59 and the gas flow path 61 of the internal electrode 60 and the gas blow-out pipe 62 to the inside of the PET bottle B, the inside and outside of the PET bottle B are returned to atmospheric pressure, and the inner surface carbon film coated PET bottle is taken out. Then, replace 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 first embodiment can be used.

The high-frequency power is generally defined as 30 to 300 MHz, but is not limited thereto. Moreover, the application of these electric powers may be continuous or intermittent (pulsed).

The bias power is generally 13.56 MHz and 100 to 1000 W, but is not limited thereto. Also, this bias power application can be continuous or intermittent (
It may be pulsed).

As described above, according to the fourth embodiment, by supplying the medium gas from the bottom of the internal electrode 60 into the plastic bottle B, the gas flow from the bottom of the plastic bottle B toward the mouth can be forcibly generated. it can. For this reason, it can prevent that the residence part of gas is made in the PET bottle B. As a result, it is possible to coat the inner surface of the PET bottle B with a carbon film having good film quality with little contamination and having a uniform film thickness.

Further, a gas blowing pipe 62 made of an insulating material with a medium gas inserted into the bottom of the internal electrode 60.
By blowing out the air, the concentration of the plasma in the vicinity of the gas blowing tube 62 can be prevented and the density of the plasma generated in the plastic bottle B can be made uniform as in the first embodiment. As a result, it is possible to coat the inner surface of the PET bottle B with a carbon film having a good film quality with little powder mixing and a uniform film thickness.

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

Therefore, an inner surface carbon film-coated PET bottle with excellent barrier properties that prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water) can be produced more mass-produced.

Similarly, unnecessary plasma is generated between the gas supply pipe 59 to which high-frequency power is applied and the grounded exhaust pipe 52 (that is, in the exhaust pipe 52), and the coating efficiency of the carbon film is lowered. For this reason, the earth shield pipe 72 is arranged on the outer periphery of the gas supply pipe 59 so as to be positioned in the gas exhaust pipe 52 in the vicinity of the mouth of the plastic bottle B, and this earth shield pipe 7
2 is grounded through the flange pipe 71 that supports it, and even if high-frequency power is supplied to the gas supply pipe 59 that penetrates the earth shield pipe 72, the inside of the exhaust pipe 52 that is the exhaust path of the medium gas Therefore, generation of unnecessary plasma can be prevented. As a result, it is possible to prevent consumption of high-frequency power accompanying unnecessary plasma generation.
The regular plasma generation efficiency can be increased, and the coating speed of the carbon film can be improved.

Furthermore, the shape of the member covering the mouth and shoulder of PET bottle B is complicated, but by forming the spacer 49 corresponding to these members from a dielectric material such as plastic that can be injection molded, Compared to the conventional case where all the members including these members are constituted by external electrodes, it can be manufactured easily. In addition, the entire apparatus can be reduced in weight compared to the conventional case where all of these members are formed of external electrodes with a conductive material such as metal. In addition, by forming the spacer 49 from a dielectric material such as plastic or soft ceramic, when the complicated mouth and shoulder of the plastic bottle B come into contact with each other, it is possible to prevent the spot from being damaged. Can do.

In the fourth embodiment, the gas blowing portion made of the insulating material is constituted by the gas blowing tube 62 made of the insulating material shown in FIG. 8, but the present invention is not limited to this. For example, FIGS.
The gas blowout part made of an insulating material is composed of a cap made of an insulating material such as plastic or ceramic in which a gas blowout hole is opened in the central axis direction. It may be attached to the bottom of the internal electrode so as to communicate with the gas flow path. In such a configuration, a gas blowing hole may be opened in the side wall of the cap.

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

(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;
FIG. 10 is an enlarged cross-sectional view showing the vicinity of the internal electrode of FIG.

Cylindrical support members 82 having flanges 81 a and 81 b at the upper and lower ends are placed on an annular base 83. A cylindrical metal external electrode body 84 is disposed in 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 external electrode body 84 and the external electrode bottom member 85 constitute a bottomed cylindrical external electrode 86 having a space of a size capable of installing a plastic container (for example, a plastic bottle) B that forms a carbon film. The disk-shaped insulator 87 is disposed between the base 83 and the external electrode bottom member 85.

The external electrode bottom member 85, the disk-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) to open and close the bottom of the external electrode main body 84. To do.

The annular insulating member 88 is placed on the upper surface of the external electrode 86 so that the upper surface of the annular insulating member 88 is flush with the upper flange 81 a of the cylindrical support member 82. Up and down flange 8
A gas exhaust pipe 90 having 9 a and 89 b is placed on the upper flange 81 a 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 screws (not shown) from the lower flange 89 b of the exhaust pipe 90 to the upper flange 81 a of the support member 82. Further, a screw (not shown) is connected to the annular insulating portion 88 from the lower flange 89b of the exhaust pipe 90.
And the exhaust pipe 90 is fixed to the annular insulating member 88 and the external electrode 86, and the annular insulating member 88 is fixed to the external electrode 86. Is also fixed. The exhaust pipe 90, the annular insulating member 88, and the external electrode 86 are fixed to each other by a mounting structure in which the exhaust pipe 90 and the external electrode 86 are not electrically connected by screws. 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 84 of the external electrode 86 through the cable 93 and the power supply terminal 94. The matching unit 95 is interposed in the cable 93 between the bias power source 92 and the power supply terminal 94.

A lid body 97 having an insulating ring 96 at the center and grounded is hermetically fixed to the upper flange 89a of the gas exhaust pipe 90. The casing 98 is attached on the lid body 97.

A 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 from the inside of the housing 98 to the lid body 97.
And is inserted into the body 84 of the external electrode 86 through the gas exhaust pipe 90 (in the portion corresponding to the central portion of the plastic bottle B to be inserted). 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.

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

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

The internal electrode 102 is made of a metal material having heat resistance such as tungsten or stainless steel, but may be made of aluminum. Further, if the surface of the internal electrode 102 is smooth, the carbon film deposited on the surface of the internal electrode 102 may be easily peeled off. For this reason, it is preferable that the surface of the internal electrode 102 is previously sandblasted to increase the surface roughness and make it difficult to peel off the carbon film deposited on the surface.

The flange pipe 106 and the earth shield pipe 10 connected to the lower end of the flange pipe 106
7 is a plastic bottle B in the main body 84 of the gas exhaust pipe 90 and the external electrode 86.
It arrange | positions so that the said gas supply pipe | tube 100 part located in the location corresponding to the center part of may be covered.

The lower end of the earth shield tube 107 is connected to the internal electrode 1 as shown in FIGS.
A desired gap g is provided from the upper end of 02. The length of this gap g is 2
It is preferable to make it 0-30 mm. For example, the insulating tube 108 made of a plastic such as polytetrafluoroethylene or polypropylene has the gas supply pipe located in a region where the internal electrode 102 and the lower end of the earth shield tube 107 are separated from each other (gap g region). 100 is entirely covered including 100.

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 body 97 grounded through the flange pipe 106.

The high-frequency power source 109 is connected to the side surface of the gas supply pipe 100 that also serves as a terminal for high-frequency power through a cable 110 and a power supply terminal 111. The matching unit 112 is interposed in the cable 110 between the high-frequency power source 109 and the power supply terminal 111.

Next, a method for producing an inner surface carbon film-coated plastic container will be described using the carbon film forming apparatus shown in FIG.

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 main body 84. Subsequently, after the plastic container, for example, the plastic bottle B is opened from the bottom side of the external electrode body 84 opened from the mouth side of the bottle B, the external electrode bottom member 85 is placed on the bottom side of the external electrode body 84 by a pusher (not shown). By attaching the disk-shaped insulator 87 and the base 83 in this order, as shown in FIG. 9, the plastic bottle B is connected to the external electrode 86 composed of the external electrode main body 4 and the external electrode bottom member 5.
Store in the interior space. At this time, the plastic bottle B communicates with the exhaust pipe 90 through its mouth.

Subsequently, the gas inside and outside the exhaust pipe 90 and the PET 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 supplied to the gas flow path 103 of the internal electrode 102 through the gas introduction pipe 99 and the gas supply pipe 100, and enters the plastic bottle B from the gas blowing hole 104 of the cap 105 attached to the bottom of the internal electrode 102. Blow out. This medium gas further flows toward the mouth of the plastic bottle B. Subsequently, 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 unit 95 and the power supply terminal 94. Thereafter, or simultaneously, high-frequency power is supplied from the high-frequency power source 109 to the gas supply pipe 100 through the cable 110, the matching unit 112 and the power supply terminal 111, and the high-frequency power is supplied to the internal electrode 102 through the gas supply pipe 100. . At this time, plasma is generated around the internal electrode 102. Since the exhaust pipe 90 located above the external electrode 86 is grounded, the exhaust pipe 90
Can be applied from the external electrode 86 toward the internal electrode 102, that is, toward the generated plasma.

As a result, a) When using high-frequency power, a high electron density is obtained compared to high-frequency power, particularly under low gas pressure conditions, so that the collision frequency with the medium gas is increased and the film-forming seed density can be increased.
b) Since the potential difference from the plasma potential can be varied by adjusting the bias power, the ion energy incident on the inner surface of the PET bottle B can be adjusted. c) Since the ion density is proportional to the electron density, it is used in combination with the above potential difference adjustment. By doing so, the ion flux incident on the inner surface of the plastic bottle B can be controlled. Bias power is applied to the film-forming species obtained 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 applying the bias voltage to the internal electrode 102. A uniform carbon film with 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 source 109 to the gas supply pipe 100,
Similarly, unnecessary plasma is generated between the grounded exhaust pipe 90 (that is, in the exhaust pipe 90), and the coating efficiency of the carbon film is lowered. As a countermeasure, an earth shield pipe 107 is arranged on the outer periphery of the gas supply pipe 100, and the earth supply pipe penetrating the earth shield pipe 107 is grounded through a flange pipe 106 supporting the earth shield pipe 107. Even when high-frequency power is supplied to the tube 100, generation of unnecessary plasma is prevented in the exhaust tube 90, which is a medium gas exhaust path. As a result, it is possible to prevent consumption of high-frequency power accompanying unnecessary plasma generation, so that regular plasma generation efficiency in the PET bottle B can be increased.

By disposing the earth shield pipe 107 on the outer periphery of the gas supply pipe 100, unnecessary plasma generation can be prevented. On the other hand, between 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 discharge occurs and the plasma density at that location increases, contamination (powder) is mixed into the inner surface of the PET bottle B or the film thickness becomes non-uniform. As a countermeasure, 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.
8 is a region where at least the internal electrode 102 and the lower end of the earth shield tube 107 are separated (
By covering the portion of the gas supply pipe 100 located in the region of the gap g), the density of plasma generated in the PET bottle B is made uniform by preventing discharge at the location.

After the carbon film reaches a predetermined thickness, the bias power source 92 and the high-frequency power source 1
The supply of bias power and high-frequency power from 09 is stopped, the supply of the medium gas is stopped, the residual gas is exhausted, and the exhaust of the gas is stopped. Then, nitrogen, rare gas, air, or the like is supplied to the gas introduction pipe 99 through the gas supply pipe 100 and the gas flow path 103 of the internal electrode 102 and the gas blowing hole 104 to be supplied into the plastic bottle B, and the inside and outside of the plastic bottle B are returned to the atmospheric pressure.
Take out the inner carbon film coated PET bottle. After that, according to the order described above, plastic bottle B
And move on to the next PET bottle coating operation.

The medium gas is basically hydrocarbon, for example, alkanes such as methane, ethane, propane, butane, pentane and hexane; alkenes such as ethylene, propylene, butene, pentene and butadiene; alkynes such as acetylene; benzene, Aromatic hydrocarbons such as toluene, xylene, 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; methyl Nitrogen-containing hydrocarbons such as amine, ethylamine and aniline can be used, and other carbon monoxide and carbon dioxide can also be used.

The high-frequency power is generally defined as 30 to 300 MHz, but is not limited thereto. Moreover, the application of these electric powers may be continuous or intermittent (pulsed).

The bias power is generally 13.56 MHz and 100 to 1000 W, but is not limited thereto. Also, this bias power application can be continuous or intermittent (
It may be pulsed).

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

Further, the earth shield pipe 107 is arranged on the outer periphery 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 pipe 100 penetrating the earth shield pipe 107 is made high. Even if high-frequency power is supplied, it is possible to prevent unnecessary plasma from being generated in the exhaust pipe 90 that is the exhaust path of the medium gas. As a result, it is possible to prevent consumption of high-frequency power accompanying unnecessary plasma generation, so that 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 a region (gap) between the internal electrode 102 and the lower end of the earth shield tube 107. By covering the portion of the gas supply pipe 100 located in the region g), it is possible to prevent discharge from occurring between 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. Bottle B
It is possible to generate a plasma with a uniform density inside, and to coat a carbon film having a uniform film thickness with a good film quality with little powder mixing on the inner surface.

Therefore, an inner surface carbon film-coated PET bottle with excellent barrier properties that prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water) can be produced more mass-produced.

(Sixth embodiment)
FIG. 11 is a cross-sectional view showing the carbon film forming apparatus on the inner surface of the plastic container according to the sixth embodiment. In FIG. 11, the same members as those in FIG. 9 referred to in the fifth embodiment described above are denoted by the same reference numerals, and the description thereof is omitted.

This carbon film forming apparatus includes a spacer 114 having a hollow portion 113 that covers a mouth portion and a shoulder portion of the plastic bottle B, and an external electrode main body 115 and an external electrode that cover other portions of the plastic bottle B. The external electrode 117 is composed of a bottom member 116.

Next, a method for producing an inner surface carbon film-coated plastic container will be described using the carbon film forming apparatus shown in FIG.

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 main body 84. Subsequently, after the plastic container, for example, the plastic bottle B is opened from the bottom side of the external electrode body 84 opened from the mouth side of the bottle B, the external electrode bottom member 85 is placed on the bottom side of the external electrode body 84 by a pusher (not shown). By attaching the disk-shaped insulator 87 and the base 83 in this order, the cavity 1 of the cylindrical spacer 114 whose shoulder from the mouth of the plastic bottle B is made of a dielectric material as shown in FIG.
13, the bottom side from the shoulder of the bottle B is accommodated in the external electrode 117. At this time, the plastic bottle B communicates with the exhaust pipe 90 through its mouth.

Subsequently, the gas inside and outside the exhaust pipe 90 and the PET 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 supplied to the gas flow path 103 of the internal electrode 102 through the gas introduction pipe 99 and the gas supply pipe 100, and enters the plastic bottle B from the gas blowing hole 104 of the cap 105 attached to the bottom of the internal electrode 102. Blow out. This medium gas further flows toward the mouth of the plastic bottle B. Subsequently, 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 unit 95 and the power supply terminal 94. Thereafter, or simultaneously, high-frequency power is supplied from the high-frequency power source 109 to the gas supply pipe 100 through the cable 110, the matching unit 112 and the power supply terminal 111, and the high-frequency power is supplied to the internal electrode 102 through the gas supply pipe 100. . At this time, plasma is generated around the internal electrode 102. The earth shield pipe 107 is disposed on the outer periphery of the gas supply pipe 100 so as to be located in the spacer 114 and in the gas exhaust pipe 90 in the vicinity of the spacer 114 and is grounded through the flange pipe 106. Using the earth shield tube 107 as a reference potential, a bias voltage can be applied from the external electrode 86 toward the internal electrode 102, that is, toward the generated plasma.

As a result, a) When using high-frequency power, a high electron density is obtained compared to high-frequency power, particularly under low gas pressure conditions, so that the collision frequency with the medium gas is increased and the film-forming seed density can be increased.
b) Since the potential difference from the plasma potential can be varied by adjusting the bias power, the ion energy incident on the inner surface of the PET bottle B can be adjusted. c) Since the ion density is proportional to the electron density, it is used in combination with the above potential difference adjustment. By doing so, the ion flux incident on the inner surface of the plastic bottle B can be controlled. Bias power is applied to the film-forming species obtained 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 applying the bias voltage to the internal electrode 102. A uniform carbon film with 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 carbon film reaches a predetermined thickness, the bias power source 92 and the high-frequency power source 1
The supply of bias power and high-frequency power from 09 is stopped, the supply of the medium gas is stopped, the residual gas is exhausted, and the exhaust of the gas is stopped. Then, nitrogen, rare gas, air, or the like is supplied to the gas introduction pipe 99 through the gas supply pipe 100 and the gas flow path 103 of the internal electrode 102 and the gas blowing hole 104 to be supplied into the plastic bottle B, and the inside and outside of the plastic bottle B are returned to the atmospheric pressure.
Take out the inner carbon film coated PET bottle. After that, according to the order described above, plastic bottle B
And 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-frequency power is generally defined as 30 to 300 MHz, but is not limited thereto. Moreover, the application of these electric powers may be continuous or intermittent (pulsed).

The bias power is generally 13.56 MHz and 100 to 1000 W, but is not limited thereto. Also, this bias power application can be continuous or intermittent (
It may be pulsed).

As described above, according to the sixth embodiment, the film-forming species obtained when the medium gas is dissociated with the plasma by drawing the plasma into the external electrode 86 by generating the plasma and applying a bias voltage to the internal electrode 102. A uniform carbon film with a uniform thickness can be coated at a high speed on the inner surface of the PET bottle B in the external electrode 86 to which a bias power is applied.

Further, by arranging the earth shield pipe 107 on the outer periphery of the gas supply pipe 100 and grounding the earth shield pipe 107 through the flange pipe 106 supporting the earth shield pipe 107, the earth shield pipe 107 as described in detail in the fifth embodiment. Even when high-frequency power is supplied to the gas supply pipe 100 penetrating the inside 107, 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, since it is possible to prevent the consumption of high-frequency power accompanying unnecessary plasma generation, the regular plasma generation efficiency in the PET bottle B is increased,
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 a region (gap) between the internal electrode 102 and the lower end of the earth shield tube 107. By covering the portion of the gas supply pipe 100 located in the region g), as described in detail in the fifth embodiment, between the lower end of the ground shield pipe 107 and the upper end of the internal electrode 102 to which high-frequency power is supplied. In the PET bottle B, it is possible to prevent a discharge from being generated, so that a uniform density plasma can be generated in the PET bottle B, and the inner surface of the film can be coated with a carbon film having a uniform film thickness with good film quality with little powder contamination. it can.

Therefore, an inner surface carbon film-coated PET bottle with excellent barrier properties that prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated drinking water) can be produced more mass-produced.

In addition, although the shape of the member covering the mouth portion and the shoulder portion of the plastic bottle B is complicated, by forming the spacer 114 corresponding to these members by a dielectric material such as plastic capable of injection molding, Compared to the conventional case where all the members including these members are constituted by external electrodes, it can be manufactured easily. In addition, the entire apparatus can be reduced in weight compared to the conventional case where all of these members are formed of external electrodes with a conductive material such as metal. In addition, by forming the spacer 114 from a dielectric material such as plastic or soft ceramic, it is possible to prevent scratches from occurring when the complicated mouth and shoulder of the plastic bottle B come into contact with each other. Can do.

In the sixth embodiment, the columnar spacer 114 made of a dielectric material having the cavity 113 is inserted and fixed to the upper part of the external electrode 86 so as to correspond to the shoulder from the mouth of the plastic bottle B. A thin film made of a dielectric material may be extended from the shoulder of the bottle B to the bottom.

As described above, the carbon film forming apparatus on the inner surface of the plastic container according to the present invention has a good film quality, a carbon film having a uniform film thickness is coated on the inner surface, and has an excellent barrier property against oxygen and carbon dioxide. Suitable for manufacturing plastic containers.

Sectional drawing which shows the carbon film formation apparatus to the inner surface of the plastic container which concerns on 1st Embodiment of this invention. The expanded sectional view which shows the internal electrode of FIG. Sectional drawing which shows the modification of the internal electrode integrated in the carbon film formation apparatus to the inner surface of the plastic container which concerns on 1st Embodiment of this invention. Sectional drawing which shows the carbon film formation apparatus to the inner surface of the plastic container which concerns on 2nd Embodiment of this invention. The expanded sectional view which shows the internal electrode of FIG. Sectional drawing which shows the modification of the internal electrode integrated in the carbon film formation apparatus to the inner surface of the plastic container which concerns on 2nd Embodiment of this invention. Sectional drawing which shows the carbon film formation apparatus to the inner surface of the plastic container which concerns on 3rd Embodiment of this invention. Sectional drawing which shows the carbon film formation apparatus to the inner surface of the plastic container which concerns on 4th Embodiment of this invention. Sectional drawing which shows the carbon film formation apparatus to the inner surface of the plastic container which concerns on 5th Embodiment of this invention. FIG. 10 is an enlarged cross-sectional view showing the vicinity of an internal electrode in FIG. 9. Sectional drawing which shows the carbon film formation apparatus to the inner surface of the plastic container which concerns on 6th Embodiment of this invention. Sectional drawing which shows the carbon film formation apparatus to the inner surface of the conventional 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 electrode 10, 52, 90 Exhaust pipe 13, 55 High frequency power supply 17 , 59, 100 Gas supply pipe 18, 60, 102 Internal electrode 20, 62 Gas blowout pipe 21 Gas blowout hole 22 Cap made of insulating material 23, 63, 92 Bias power supply 31, 72, 107 Earth shield pipe 32, 73, 109 High-frequency power supply 49, 114 Cylindrical spacer 108 Insulating tube B PET bottle

Claims (13)

An external electrode having a size that surrounds the outer periphery of the plastic container when the plastic container to be processed is inserted;
An exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located;
An internal electrode inserted from the exhaust pipe side into the plastic container in the external electrode and connected to the ground side;
An exhaust means attached to the exhaust pipe;
Gas supply means for supplying a medium gas to the internal electrode;
A high-frequency power source connected to the external electrode;
Comprising
The internal electrode is provided with a gas blowing portion made of an insulating material for blowing a medium gas at a portion located on the bottom side of the plastic container inserted into the external electrode. Carbon film forming device. In producing an inner surface carbon film-coated plastic container using the carbon film forming apparatus according to claim 1,
(A) inserting a plastic container as an object to be processed into the external electrode;
(B) An internal electrode provided with a gas blowing portion made of an insulating material is connected to the inside of the plastic container from an exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located. Inserting the gas blowing portion so as to be positioned on the bottom side of the container;
(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 to the internal electrode by the gas supply means, and the medium gas is supplied from the gas blowing portion of the internal electrode into the plastic container. Blowing the gas and setting the inside of 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 electrode, generating plasma around the internal electrode located in the plastic container, and dissociating the medium gas by the plasma to form a carbon film on the inner surface of the plastic container And a method for producing an inner surface carbon film-coated plastic container. An external electrode having a size surrounding the plastic container when the plastic container is processed;
An exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located;
An internal electrode inserted from the exhaust pipe side into the plastic container in the external electrode;
An exhaust means attached to the exhaust pipe;
Gas supply means for supplying a medium gas to the internal electrode;
A high-frequency power source connected to the internal electrode;
A bias power source connected to the external electrode;
Comprising
The internal electrode is provided with a gas blowing portion made of an insulating material for blowing a medium gas at a portion located on the bottom side of the plastic container inserted into the external electrode. Carbon film forming device. In producing an inner surface carbon film-coated plastic container using the carbon film forming apparatus according to claim 3,
(A) inserting a plastic container as an object to be processed into the external electrode;
(B) An internal electrode provided with a gas blowing portion made of an insulating material is connected to the inside of the plastic container from an exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located. Inserting the gas blowing portion so as to be positioned on the bottom side of the container;
(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 to the internal electrode by the gas supply means, and the medium gas is supplied from the gas blowing portion of the internal electrode into the plastic container. Blowing the gas and setting the inside of the exhaust pipe including the inside of the plastic container to a predetermined gas pressure;
(D) A high frequency power is applied from the bias power source to the external electrode, and a high frequency power is supplied from the high frequency power source to the internal electrode through the gas supply pipe to generate plasma in the plastic container. And a step of dissociating the medium gas to coat a carbon film on the inner surface of the plastic container. An external electrode having a size surrounding the plastic container when the plastic container is processed;
A spacer made of a dielectric material interposed between the external electrode and at least the mouth and shoulder of the container when the plastic container as the object to be processed is inserted;
An exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located;
An internal electrode inserted from the exhaust pipe side into the plastic container in the external electrode and connected to the ground side;
An exhaust means attached to the exhaust pipe;
Gas supply means for supplying a medium gas to the internal electrode;
A high-frequency power source connected to the external electrode;
Comprising
The internal electrode is provided with a gas blowing portion made of an insulating material for blowing a medium gas at a portion located on the bottom side of the plastic container inserted into the external electrode. Carbon film forming device. In producing an inner surface carbon film-coated plastic container using the carbon film forming apparatus according to claim 5,
(A) A plastic container, which is an object to be processed, is surrounded by an outer electrode and a spacer made of a dielectric material, and at least the outer periphery of the mouth and shoulder of the container is surrounded by the spacer. Inserting the outer periphery so as to be surrounded by the external electrode;
(B) An internal electrode provided with a gas blowing portion made of an insulating material is connected to the inside of the plastic container from an exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located. Inserting the gas blowing portion so as to be positioned on the bottom side of the container;
(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 to the internal electrode by the gas supply means, and the medium gas is supplied from the gas blowing portion of the internal electrode into the plastic container. Blowing the gas and setting the inside of 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 electrode, generating plasma around the internal electrode located in the plastic container, and dissociating the medium gas by the plasma to form a carbon film on the inner surface of the plastic container And a method for producing an inner surface carbon film-coated plastic container. An external electrode having a size surrounding the plastic container when the plastic container is processed;
A spacer made of a dielectric material interposed between at least the mouth and shoulder of the container and the external electrode when the plastic container as the object to be processed is inserted;
An exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located;
An internal electrode inserted into the plastic container in the external electrode;
A gas supply pipe having one end connected to the internal electrode and the other end also serving as a power supply terminal extending toward the exhaust pipe;
An earth shield pipe disposed at least on the outer periphery of the gas supply pipe portion located in the external electrode and in the exhaust pipe near the mouth of the container, and grounded;
An exhaust means attached to the exhaust pipe;
Gas supply means for supplying a medium gas to the gas supply pipe;
A high-frequency power source connected to the gas supply pipe;
A bias power source connected to the external electrode;
The plastic container is characterized in that the internal electrode is provided with a gas blowing portion made of an insulating material for blowing out a medium gas at a portion located on the bottom side of the plastic container inserted into the external electrode. Carbon film forming device on the inner surface. In producing an inner surface carbon film-coated plastic container using the carbon film forming apparatus according to claim 7,
(A) A plastic container, which is an object to be processed, is surrounded by an outer electrode and a spacer made of a dielectric material, and at least the outer periphery of the mouth and shoulder of the container is surrounded by the spacer. Inserting the outer periphery so as to be surrounded by the external electrode;
(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 blowing portion made of an insulating material is connected to the inside of the plastic container from an exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located. Inserting the blowout part so as to be located on the bottom side of the container;
(C) After exhausting the gas inside and outside the container through the exhaust pipe by the exhaust pipe means, medium gas is supplied from the gas supply pipe means to the internal electrode through the gas supply pipe, and from the gas blowing portion of the internal electrode Blowing a medium gas into the plastic container to set the inside of the exhaust pipe including the inside of the plastic container to a predetermined gas pressure;
(D) A high frequency power is applied from the bias power source to the external electrode, and a high frequency power is supplied from the high frequency power source to the internal electrode through the gas supply pipe to generate plasma in the plastic container. And a step of dissociating the medium gas to coat a carbon film on the inner surface of the plastic container. The gas blowing portion is further provided in a side surface region in the vicinity of the internal electrode portion located on the bottom side of the plastic container inserted into the external electrode.
7. The apparatus for forming a carbon film on the inner surface of the plastic container according to any one of 7 above. An external electrode having a size surrounding the plastic container when the plastic container is processed;
An exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located;
An internal electrode that is 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;
A gas supply pipe having one end connected to the internal electrode and the other end also serving as a power supply terminal extending toward the exhaust pipe;
An earth shield pipe having a tip disposed on the outer periphery of the gas supply pipe portion located at least in the external electrode and in the exhaust pipe in the vicinity of the mouth of the container with a desired gap from the internal electrode and grounded;
An insulating tube coated at least on the gas supply pipe located in a gap region between the internal electrode and the tip of the earth shield pipe;
An exhaust means attached to the exhaust pipe;
Gas supply means for supplying a medium gas to the gas supply pipe;
A high-frequency power source connected to the gas supply pipe;
A device for forming a carbon film on the inner surface of a plastic container, comprising: a bias power source connected to the external electrode. In producing an inner surface carbon film-coated plastic container using the carbon film forming apparatus according to claim 10,
(A) inserting a plastic container as an object to be processed into the 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 an internal electrode provided with a gas blowing portion is connected to the external side on the side where the mouth of the container is located. Inserting into the plastic container from an exhaust pipe attached to the end face of the electrode 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 from the gas blowing portion of the internal electrode into the plastic container Blowing out the medium gas and setting the inside of the exhaust pipe including the inside of the plastic container to a predetermined gas pressure;
(D) A high frequency power is applied from the bias power source to the external electrode, and a high frequency power is supplied from the high frequency power source to the internal electrode through the gas supply pipe to generate plasma in the plastic container. And a step of dissociating the medium gas to coat a carbon film on the inner surface of the plastic container. An external electrode having a size surrounding the plastic container when the plastic container is processed;
A spacer made of a dielectric material interposed between at least the mouth and shoulder of the container and the external electrode when the plastic container as the object to be processed is inserted;
An exhaust pipe attached via an insulating member to the end face of the external electrode on the side where the mouth of the container is located;
An internal electrode that is 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;
A gas supply pipe having one end connected to the internal electrode and the other end also serving as a power supply terminal extending toward the exhaust pipe;
An earth shield pipe having a tip disposed on the outer periphery of the gas supply pipe portion located at least in the external electrode and in the exhaust pipe in the vicinity of the mouth of the container with a desired gap from the internal electrode and grounded;
An insulating tube coated at least on the gas supply pipe located in a gap region between the internal electrode and the tip of the earth shield pipe;
An exhaust means attached to the exhaust pipe;
Gas supply means for supplying a medium gas to the gas supply pipe;
A high-frequency power source connected to the gas supply pipe;
A device for forming a carbon film on the inner surface of a plastic container, comprising: a bias power source connected to the external electrode. In producing an inner surface 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 processed, is surrounded by an outer electrode and a spacer made of a dielectric material, and at least the outer periphery of the mouth and shoulder of the container is surrounded by the spacer. Inserting the outer periphery so as to be surrounded by the 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 an internal electrode provided with a gas blowing portion is connected to the external side on the side where the mouth of the container is located. Inserting into the plastic container from an exhaust pipe attached to the end face of the electrode 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 from the gas blowing portion of the internal electrode into the plastic container Blowing out the medium gas and setting the inside of the exhaust pipe including the inside of the plastic container to a predetermined gas pressure;
(D) A high frequency power is applied from the bias power source to the external electrode, and a high frequency power is supplied from the high frequency power source to the internal electrode through the gas supply pipe to generate plasma in the plastic container. And a step of dissociating the medium gas to coat a carbon film on the inner surface of the plastic container.

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