KR100685594B1 - Apparatus for forming carbon film on inner surface of plastic container and method of manufacturing plastic container having inner surface coated with carbon film - Google Patents

Abstract

A bottomed cylindrical external electrode having a size surrounding the outer periphery of the container when the plastic container to be processed is inserted, except at the inlet and the shoulder of the container, and at least the inlet and the shoulder of the container when the container is inserted; A spacer made of a dielectric material interposed between the portion and the external electrode, an exhaust pipe attached to an end surface of the external electrode on the side where the inlet of the container is located through an insulating member, and the exhaust pipe in the container in the external electrode. The inner electrode which is inserted over the entire length of the vessel from the side and connected to the ground side, and has a gas injection hole for injecting the medium gas, an exhaust means attached to the exhaust pipe, and the medium gas to the inner electrode. Gas supply means for supplying, and a high frequency power source connected to the external electrode.

Description

A carbon film forming apparatus on the inner surface of a plastic container and a manufacturing method of an inner carbon film-coated plastic container

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

Fig. 2 is a characteristic diagram showing the thickness of the carbon film from the inlet portion to the bottom portion of a PET bottle in Example 1 and Example 2 according to the first embodiment,

3 is a schematic cross-sectional view showing a carbon film forming apparatus on an inner surface of a plastic container according to a second embodiment of the present invention;

Fig. 4 is a characteristic diagram showing a change in bias voltage with respect to the internal electrode when constant high frequency power is applied to the external electrode in Example 3 according to the second embodiment and the gas pressure in the PET bottle and the exhaust pipe is changed.

Fig. 5 is a characteristic diagram showing a change in bias voltage with respect to the internal electrode when constant high frequency power is applied to the external electrode in Example 4 and the gas pressure in the PET bottle and the exhaust pipe is changed;

6 is a characteristic diagram showing a change in the bias voltage with respect to the internal electrode when the gas pressure in the PET bottle and the exhaust pipe is made constant in Example 5 according to the second embodiment, and the high frequency power applied to the external electrode is changed;

7 is a characteristic diagram showing a change in the bias voltage with respect to the internal electrode when the gas pressure in the PET bottle and the exhaust pipe in Example 6 is made constant and the high frequency power applied to the external electrode is changed;

8 is a schematic cross-sectional view showing a carbon film forming apparatus on an inner surface of a plastic container according to a third embodiment of the present invention;

9 is an enlarged cross-sectional view of a main portion of the carbon film forming apparatus of FIG. 8;

FIG. 10 shows the internal electrode in Example 7 according to the third embodiment, when constant high frequency power is applied to the external electrode and constant high frequency power is applied to the internal electrode, and the gas pressure in the PET bottle and the exhaust pipe is changed. Characteristic diagram showing a change in bias voltage with respect to

11 is a cross-sectional view showing a carbon film forming apparatus on an inner surface of a plastic container according to a fourth embodiment of the present invention;

12 is a cross-sectional view showing a modification of the carbon film forming apparatus on the inner surface of the plastic container according to the fourth embodiment of the present invention;

13 is a characteristic diagram showing the thickness of the carbon film from the inlet portion to the bottom portion of a PET bottle in Examples 8 and 9 according to the fourth embodiment;

14 is a cross-sectional view showing a carbon film forming apparatus on an inner surface of a plastic container according to a fifth embodiment of the present invention;

FIG. 15 is a sectional view of principal parts of the ground shield pipe of FIG. 14; FIG.

FIG. 16 is a sectional view showing the principal parts of still another form of the ground shield tube of FIG. 14; FIG.

17 is an equivalent circuit diagram of a power supply system provided in a carbon film forming apparatus on an inner surface of a plastic container according to a sixth embodiment of the present invention.

18 is a cross-sectional view showing a carbon film forming apparatus on a conventional plastic container inner surface.

※ Explanation of symbols about main part of drawing ※

2: support member 3: expectation

6 external electrode 7 insulator

8: cavity 9: spacer

12 gas exhaust pipe 13 branch gas exhaust pipe

14 cover structure 15 high frequency power supply

The present invention relates to a carbon film forming apparatus on the inner surface of a plastic container and a manufacturing method of the inner surface carbon film coated plastic container.

Plastic containers, such as PET bottles, have been attempted to coat carbon films such as diamond like carbon (DLC) on their inner surfaces to prevent permeation of oxygen from outside and permeation of carbon dioxide from inside (eg, carbonated beverages).

As a method of coating a carbon film on the inner surface of such a plastic container, a method using high frequency plasma is disclosed in Japanese Patent Laid-Open No. 1996-53116 and Japanese Patent No. 2788412 (Japanese Laid-Open Patent Publication No. 1996-53117). Japanese Patent Laid-Open No. 1997-272567 discloses a method of coating a carbon film on a film using high frequency plasma as an application method. Patent 3072269 (Japanese Patent Laid-Open No. 1998-226884) discloses a coating method of a carbon film corresponding to a special shaped container. Patent 3115252 (Japanese Patent Laid-Open No. 1998-258825) and the like disclose a method of simultaneously coating a plurality of containers as a mass production technique. In addition, the disclosed technology of coating a carbon film on a plastic container is disclosed in "K. Takemoto, et al, Proceedings of ADC / FCT '99, p 285 ', E, Shimamura et al, 10t years IAPRI World Conference 1997, p 251.

Patent No. 2788412 (Japanese Patent Application Laid-Open No. 1996-53116), 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. 18 is a cross-sectional view of a carbon film coating apparatus on a plastic container using high frequency plasma CVD described in this publication.

The external electrode 201 is provided on the mount 202 via a seal plate 203 made of, for example, polytetrafluoroethylene. This external electrode 201 has an inner shape that is almost similar in appearance to the outer shape of a plastic container, for example, a PET bottle B, which is housed. It is preferable that this external electrode 201 is also an inner shape according to the screw shape for bottle caps. The said external electrode 201 is comprised from the normal main body 201a and the stopper part 201b attached to the upper end of this main body 201a, and serves as a vacuum container. The gas exhaust pipe 204 communicates with the lower portion of the external electrode 201 through the mount 202 and the seal plate 203.

The internal electrode 205 is inserted into the PET bottle B housed in the external electrode 201. The internal electrode 205 has an air structure, and a plurality of gas injection holes 206 are formed on the surface thereof. A gas supply pipe 207 for supplying a CVD medium gas is in communication with the lower end of the internal electrode 205 through the mount 202 and the seal plate 203. The CVD medium gas is supplied into the internal electrode 205 through the supply pipe 207, and is supplied into the bottle B from the gas injection hole 206.

The RF input terminal 208 is connected to the lower portion of the external electrode 201 via the mount 202 and the seal plate 203. The RF input terminal 208 is electrically insulated from the mount 202. The lower end of the RF input terminal 208 is connected to the high frequency power supply 210 via the matching unit 209. The external electrode 201 receives high frequency power for plasma generation from the high frequency power supply 210 through the matcher 209 and the RF input terminal 208.

The method of coating a carbon film on PET bottle using the apparatus of such a structure is demonstrated.

First, the bottle B is hermetically sealed in the external electrode 201 by inserting a PET bottle B into the main body 201a of the external electrode 201 and attaching a stopper 201b to the main body 201a. I store it. 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. After reaching the prescribed vacuum degree (typical value: 10 ^-2 to 10 ^-5 Torr), the medium gas is supplied to the internal electrode 205 through the gas supply pipe 207 at a flow rate of, for example, 10 to 50 mL / min. The supplied medium gas is also injected into the bottle B through the gas injection hole 206 of the internal electrode 205. As the medium gas, for example, aliphatic hydrocarbons such as benzene, toluene, xylene and cyclohexane, aromatic hydrocarbons, oxygen-containing hydrocarbons and nitrogen-containing hydrocarbons are used. The pressure in the bottle B is set to, for example, 2 × 10 ⁻¹ to 1 × 10 ⁻² Torr by the balance between the gas supply amount and the exhaust amount. Thereafter, high frequency power of 50 to 1000 W is applied from the high frequency power supply 210 to the external electrode 201 through the matching unit 209 and the RF input terminal 208.

By the application of the 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 bottle B is accommodated in the external electrode 201 with almost no gap, plasma is generated in the bottle B. The medium gas is dissociated or further ionized by the plasma to produce a film forming species for forming a carbon film. 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 film thickness, application of high frequency power is stopped. In addition, the supply of the medium gas, the exhaust of residual gas, nitrogen, rare gas, or air is supplied into the external electrode 201 to return the inside of the space to atmospheric pressure. Next, the bottle B was removed from the external electrode 201. In this method, it takes 2 to 3 seconds to form the carbon film at a thickness of 30 nm.

In the coating method using such a high frequency plasma, the thickness of the carbon film in the region extending from the inlet portion of the inner surface of the plastic container to the shoulder portion and the shoulder portion becomes thicker than that of the other inner surface portions of the container. For this reason, the problem that uniform coating becomes difficult arises.

An object of the present invention is to provide a carbon film forming apparatus on an inner surface of a plastic container capable of coating a carbon film having a uniform film thickness on the entire inner surface of a plastic container.

An object of the present invention is to provide a method for producing a plastic container coated with an inner surface of a carbon film having a uniform film thickness.

An object of the present invention is to provide a carbon film forming apparatus on an inner surface of a plastic container that can coat a carbon film having a good film quality and a uniform film thickness on an inner surface of a plastic container.

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

An object of the present invention is to provide an apparatus for forming a carbon film on an inner surface of a plastic container capable of expressively coating a carbon film having a good film quality and having a uniform film thickness on the inner surface of a plastic container.

An object of the present invention is to provide a method for producing a plastic container in which a carbon film having good film quality and having a uniform film thickness is highway coated on an inner surface thereof.

According to this invention, the carbon film forming apparatus and the manufacturing method of a plastic container to the inner surface of a plastic container demonstrated below are provided.

(1) a bottomed cylindrical external electrode having a size surrounding the outer periphery except for the inlet and the shoulder of the container when the plastic container to be processed is inserted;

A spacer made of a dielectric material interposed between at least an inlet and a shoulder of the container and the external electrode when the container is inserted;

An exhaust pipe installed through an insulating member on an end surface of the external electrode on the side where the inlet of the container is located;

An inner electrode inserted into the vessel in the outer electrode from the exhaust pipe side over the entire length of the vessel, connected to the ground side, and having a gas injection hole for injecting a medium gas;

Exhaust means provided in the exhaust pipe,

Gas supply means for supplying a medium gas to the internal electrode;

A carbon film forming apparatus on an inner surface of a plastic container having a high frequency power source connected to the external electrode.

(2) In producing the inner surface carbon film-coated plastic container using the carbon film forming apparatus of (1) above,

(a) The outer periphery of at least the inlet part and the shoulder part of the container is enclosed in the said spacer in the bottomed cylindrical outer electrode and the spacer which consists of a dielectric material, and the plastic container which is a to-be-processed object Inserting the metal so as to be enclosed in the external electrode;

(b) from an exhaust pipe attached to the bottom or side region or both sides thereof with through holes for injecting a medium gas through an insulating member on the end face of the outer electrode on the side where the inlet of the container is located; Inserting the inside of the container over approximately the entirety thereof;

(c) exhausting the gas in the container through the exhaust pipe by the exhaust pipe means, supplying the medium gas to the internal electrode by the gas supply means, and supplying the medium gas into the plastic container from the gas injection hole of the internal electrode. Spraying and setting the inside of the exhaust pipe including the inside of the plastic container to a predetermined gas pressure;

(d) applying a high frequency power from the high frequency power source to the external electrode to generate a plasma around the internal electrode located in the container, dissociating the medium gas by the plasma and coating a carbon film on the inner surface of the container; Method for producing an inner surface carbon film-covered plastic container comprising a.

(3) a bottomed cylindrical external electrode having a size surrounding the outer periphery except for the inlet and the shoulder of the container when the plastic container to be processed is inserted;

A spacer made of a dielectric material interposed between at least an inlet and a shoulder of the container and the external electrode when the container is inserted;

A conductive member attached to the end face of the spacer on the side where the inlet of the container is connected to the external electrode;

An exhaust pipe attached to an end surface of the external electrode on the side where the inlet of the container is located through an insulating member;

An inner electrode inserted into the vessel in the outer electrode from the exhaust pipe side over the entire length of the vessel and connected to the ground side, and having a gas injection hole for injecting a medium gas;

Exhaust means attached to the exhaust pipe,

Gas supply means for supplying a medium gas to the internal electrode;

A carbon film forming apparatus on an inner surface of a plastic container having a high frequency power supply connected to the external electrode and serving as a bias.

(4) In producing the inner surface carbon film-coated plastic container using the carbon film forming apparatus of (3) above

(a) The outer periphery of at least the inlet and the shoulder of the container is formed in a spacer made of a dielectric material attached in the bottomed cylindrical outer electrode and the conductive member is connected to the outer electrode. A step of inserting the outer periphery of the container portion other than that enclosed within the inner electrode;

(b) the vessel from an exhaust pipe provided with an inner electrode having a through hole for injecting a medium gas in the bottom or side region or both sides thereof through an insulating member in the end face of the outer electrode on the side where the inlet of the vessel is located; Inserting the entire length of the vessel into the interior of the

(c) exhausting the gas in the container through the exhaust pipe by the exhaust pipe means, supplying the medium gas to the internal electrode by the gas supply means, and injecting the medium gas into the container from the gas injection hole of the internal electrode. Setting the inside of the exhaust pipe including the inside of the container to a predetermined gas pressure;

(d) supplying high frequency power to the external electrode from a high frequency power source serving as a bias to generate a plasma around the internal electrode located in the container, dissociating the medium gas by the plasma to form a carbon film on the inner surface of the container. A method for producing an inner surface carbon film-coated plastic container comprising a step of coating.

(5) a bottomed cylindrical external electrode having a size surrounding the outer periphery except for the inlet and the shoulder of the container when the plastic container to be processed is inserted;

A spacer made of a dielectric material interposed between at least the inlet and shoulder portions of the container and the external electrode when the container is inserted;

A conductive member provided on the end face of the spacer on the side where the inlet of the container is connected to the external electrode;

An exhaust pipe installed through an insulating member on an end surface of the external electrode on the side where the inlet of the container is located;

An inner electrode inserted into the vessel in the outer electrode over the entire length of the vessel at the exhaust pipe side, and having a gas injection hole for injecting a medium gas;

Exhaust means attached to the exhaust pipe,

Gas supply means for supplying a medium gas to the internal electrode, a high frequency power supply connected to the internal electrode,

A carbon film forming apparatus on an inner surface of a plastic container including a bias power supply connected to the external electrode.

(6) In manufacturing the inner surface carbon film-coated plastic container using the carbon film forming apparatus of (5),

(a) The outer periphery of at least the inlet and the shoulder of the container is formed in a spacer made of a dielectric material attached in the bottomed cylindrical outer electrode and the conductive member is connected to the outer electrode. A step of inserting the outer periphery of the container portion other than that enclosed within the outer electrode;

(b) from an exhaust pipe attached to the bottom or side region or both sides thereof with an injection hole for injecting a medium gas through an insulating member on the end face of the outer electrode on the side where the inlet of the container is located; Inserting the inside of the container over the entire length of the container,

(c) exhausting the gas in the container through the exhaust pipe by the exhaust pipe means, supplying the medium gas to the internal electrode by the gas supply means, and injecting the medium gas into the container from the gas injection hole of the internal electrode. And setting the inside of the exhaust pipe including the inside of the vessel at a predetermined gas pressure,

(d) applying a high frequency power from the bias power supply to the external electrode through a matcher, while supplying a high frequency power from a high frequency power supply to the inner electrode through a matcher, thereby placing plasma around the inner electrode positioned in the vessel; And dissociating the medium gas by the plasma to coat the carbon film on the inner surface of the container.

(7) a bottomed cylindrical external electrode surrounding the container when the plastic container to be processed is inserted;

An exhaust pipe attached to an upper portion of the external electrode on the side where the inlet of the container is located;

An inner electrode inserted into the vessel in the outer electrode and serving as a gas injection tube for injecting a medium gas;

A gas supply pipe having one end connected to the internal electrode and the other end serving as a feed terminal extending to the exhaust pipe side;

A ground shield pipe disposed at and grounded at an outer periphery of the gas supply pipe portion located at least in the external electrode and in the exhaust pipe near the inlet of the container;

Exhaust means attached to the exhaust pipe,

Gas supply means for supplying a medium gas to the gas supply pipe;

A carbon film forming apparatus on an inner surface of a plastic container including a high frequency power source connected to the gas supply pipe.

(8) In producing the inner surface carbon film-coated plastic container using the carbon film forming apparatus of (7),

(a) inserting a plastic container, which is a workpiece, so as to be surrounded by a bottomed cylindrical outer electrode;

(b) A step of inserting an internal electrode serving as a tube for injecting a medium gas into the interior of the container, by connecting a gas supply pipe having a grounded ground shield disposed on the outer periphery simultaneously with or before and after the step (a). and,

(c) exhausting the gas in the container through the exhaust pipe by the exhaust pipe means, supplying the medium gas from the gas supply pipe means to the internal electrode, and injecting the medium gas into the container from the gas injection hole of the internal electrode. And setting the inside of the exhaust pipe including the inside of the vessel at a predetermined gas pressure,

(d) High frequency power is supplied from the high frequency power supply to the internal electrode through the gas supply pipe, and a high frequency power having a frequency lower than that of the high frequency power supplied from the bias power supply to the internal electrode is applied to the external electrode, thereby And producing a plasma to dissociate the medium gas by the plasma to coat a film on the inner surface of the container.

(9) a bottomed cylindrical external electrode having a size surrounding the container when the plastic container to be processed is inserted, and at least the inlet and shoulder portions of the container and the external electrode when the container is inserted; A spacer comprising a dielectric material interposed between

An exhaust pipe attached to an end surface of the external electrode on the side where the inlet of the container is located through an insulating member;

An inner electrode inserted into the container in the outer electrode and having a gas injection hole for injecting a medium gas;

Exhaust means attached to the exhaust pipe,

Gas supply means for supplying a medium gas to the gas supply pipe;

A high frequency power supply connected to the gas supply pipe through a matcher,

A bias power supply connected to the external electrode via a matcher;

An apparatus for forming a carbon film on an inner surface of a plastic container having an inductance whose one end is connected to a conductive path between the gas supply pipe and the matching device and whose other end is grounded.

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

(1st embodiment)

FIG. 1: is sectional drawing which shows the carbon film forming apparatus in the inner surface of the plastic container which concerns on 1st Embodiment.

The cylindrical support members 2 having the flanges 1a and 1b at the upper and lower ends are mounted on the annular base 3. The outer electrode main body 4 made of a cylindrical metal is disposed in the support member 2. The external electrode bottom member 5 made of disc shape is detachably attached to the bottom of the external electrode main body 4. For example, a bottomed cylindrical external electrode having a space of a size capable of installing a plastic container (for example, a PET bottle) B that forms a carbon film by the external electrode body 4 and the external electrode bottom member 5. (6) is comprised. The disc shaped insulator 7 is disposed between the base 3 and the external electrode bottom member 5.

In addition, the external electrode bottom member 5, the disc-shaped insulator 7 and the base 3 are integrally moved up and down with respect to the external electrode body 4 by a pusher (not shown). The bottom part of the external electrode main body 4 is opened and closed.

The cylindrical spacer 9 made of a dielectric material is inserted in the upper portion of the main body 4 in the external electrode 6 so that the upper end of the spacer 9 is one side with the upper end of the main body 4. It is. This spacer 9 has a cavity 8 having a shape in which a circumference and a truncated cone corresponding to the inlet and shoulder portions of a plastic container, such as a PET bottle B, inserted therein are combined. The spacer 9 is fixed by screws (not shown) screwed from the annular insulating member described later mounted thereon. In such a structure in which the spacer 9 is inserted into and fixed to the upper part of the main body 4 in the external electrode 6, when the PET bottle B is inserted from the bottom side of the external electrode 6, The inlet portion and the shoulder portion of the outer circumference of the PET bottle B are located in the cavity 8 of the spacer 9, and the outer circumference of the PET bottle B is located on the inner surface of the outer electrode 6.

As the dielectric material constituting the spacer 9, for example, plastic or ceramic is preferably used. Although various things can be used as plastics, Fluorine resins, such as polytetrafluoroethylene which are especially low in high frequency loss and excellent in heat resistance, are preferable. As the ceramic, alumina having low high frequency loss, steel tight, or Macor having high machinability are preferable.

In the annular insulating member 10, the surface of the annular insulating member 10 coincides with the upper flange 1a of the cylindrical supporting member 2 on the surfaces of the external electrode 6 and the spacer 9. It is mounted as much as possible. In the annular insulating member 10, a screw (not shown) is screwed onto the spacer 9 from the insulating member 10 to insert and fix the spacer 9 into the external electrode 6.

The gas exhaust pipe 12 which has the flange 11a, 11b up and down is mounted in the surface of the upper flange 1a of the said support member 2, and the said annular insulation member 10. As shown in FIG. The gas exhaust pipe 12 is attached to the support member 2 by screwing a screw (not shown) from the lower flange 11b of the exhaust pipe 12 to the upper flange 1a of the support member 2. It is fixed. In addition, the main body 4 of the external electrode 6 penetrates the screw (not shown) from the lower flange 11b of the exhaust pipe 12 through the annular insulator 10 and the main body of the external electrode 6. By screwing in (4), it is suspended in the said exhaust pipe 12 through the said annular insulating member 10. The exhaust pipe 12, the annular insulating member 10, and the main body 4 of the external electrode 6 are fixed to the main body 4 of the exhaust pipe 12 and the external electrode 6. It is structured so as not to be electrically connected by screws.

The branch gas exhaust pipe 13 has one end connected to the side wall of the gas exhaust pipe 12. The other end of the branch gas exhaust pipe 13 is provided with exhaust equipment such as a vacuum pump (not shown). The lid structure 14 is attached to the upper flange 11a of the exhaust pipe 12.

For example, the high frequency power supply 15 that outputs high frequency power with a frequency of 13.56 MHz is connected to the main body 4 of the external electrode 6 via the cable 16 and the power supply terminal 17. The matching unit 18 is attached to the cable 16 between the high frequency power supply 15 and the power supply terminal 17.

The gas supply pipe 19 which also serves as a ground terminal passes through the lid structure 14 and is inserted into the spacer 9 through the gas exhaust pipe 12.

The internal electrode 20 is disposed almost entirely in the longitudinal direction in the external electrode 6 and the spacer 9 (the space where the PET bottle B is inserted). An upper end of the internal electrode 20 is attached to a lower end of the gas supply pipe 19 positioned on the spacer 9 side with a detachable material. The internal flow path 21 is formed on the central axis of the internal electrode 20. The stopper 23 is attached to the bottom of the internal electrode 20 with a detachable material. The stopper 23 is provided with a gas injection hole 22 for injecting a medium gas.

In addition, the gas injection hole may be opened to communicate with the gas flow passage 21 on the lower sidewall of the internal electrode 20. In this case, the gas injection hole is preferably opened in the side region in the range of up to 25% of the length inserted into the PET bottle B at the bottom of the internal electrode 20.

The diameter of the said internal electrode 20 shall be below the metal stopper diameter of the bottle B, and the length shall be the length which can be inserted in the substantially whole of the longitudinal direction of the PET bottle B. As shown in FIG. The length is set so that the ratio with respect to the full length of PET bottle B is about {1-D / (2L)}. Where D is the inside diameter of PET bottle, L is the full length of PET bottle, and L> (D / 2).

The internal electrode 20 is made of a metal material having heat resistance such as tungsten or stainless steel, but may be made of aluminum. In addition, when the surface of the internal electrode 20 is smooth, there is a possibility that the carbon film deposited on the surface of the internal electrode 20 may be easily peeled off. For this reason, it is preferable that the surface of the internal electrode 20 is sand blasted in advance to increase the surface roughness, thereby making it difficult to peel off the carbon film deposited on the surface.

Next, the manufacturing method of an inner surface carbon film coating plastic container is demonstrated using the apparatus shown in FIG.

The bottom part of the external electrode main body 4 is opened by removing the external electrode bottom member 5, the disk-shaped insulator 7, and the base 3 by a pusher (not shown). Subsequently, a plastic container such as a PET bottle B is inserted from the bottom side of the open external electrode body 4 from the inlet side of the bottle B. Next, the external electrode bottom member 5, the disk-shaped insulator 7, and the base 3 are attached in this order to the bottom side of the external electrode body 4 by a pusher (not shown). Thereby, as shown in FIG. 1, the shoulder part is accommodated in the cavity part 8 of the cylindrical spacer 9 which consists of a dielectric material from the inlet part of PET bottle B, and the bottom part from the shoulder part of the said bottle B is carried out. The secondary side is accommodated in the external electrode 6. At this time, the PET bottle B communicates with the exhaust pipe 12 through its inlet.

Subsequently, gas inside and outside the said exhaust pipe 12 and the PET bottle B is exhausted through the branch exhaust pipe 13 and the exhaust pipe 12 by the exhaust means not shown. The medium gas is supplied to the gas flow path 21 of the internal electrode 20 through the gas supply pipe 19, and the PET bottle (from the gas injection hole 22 of the stopper 23 provided at the bottom of the internal electrode 20). B) to spray in. This medium gas further flows toward the inlet of PET bottle B. Subsequently, the gas supply amount and the gas exhaust amount are balanced, and the inside of the PET bottle B is set to a predetermined gas pressure.

Subsequently, high frequency power is supplied from the high frequency power supply 15 to the external electrode 6 through the cable 16, the matching unit 18, and the power supply terminal 17. At this time, a plasma is generated between the external electrode 6 (substantially the inner surface of the PET bottle B) and the grounded internal electrode 20. The medium gas dissociates by this plasma, and the produced film forming species is deposited on the inner surface of the PET bottle B, and a coating film (carbon film) is formed.

After the film thickness of the carbon film reaches a predetermined thickness, the supply of the high frequency power from the high frequency power supply 15 is stopped, the supply of the medium gas is stopped, the residual gas is exhausted, and the exhaust of the gas is stopped. Subsequently, nitrogen, rare gas, or air is supplied from the gas supply pipe 19 into the PET bottle B through the gas flow passage 21 of the internal electrode 20 and the gas injection hole 22 of the stopper 23. . Thereby, the inside and outside of the said PET bottle B are returned to atmospheric pressure, and the inner surface carbon film coating PET bottle is picked up. Thereafter, the PET bottles are exchanged in the above-described order, and the process moves to the next PET bottle coating operation.

As said medium gas, it is based on hydrocarbon, For example, Alkanes, such as methane, an ethane, a propane, butane, a pentane, hexane; Alkenes such as ethylene, propylene, butene, pentene and butadiene; Alkynes such as acetylene; Aromatic hydrocarbons such as benzene, toluene, xylene, indene, naphthalene and phenanthrene; Cyclo paraffins such as cyclopropane and cyclohexane; Cycloolefins such as cyclopentene and cyclohexane; Oxygen-containing hydrocarbons such as methyl alcohol and ethyl alcohol; Nitrogen containing hydrocarbons, such as methylamine, ethylamine, aniline, etc. can be used. As the medium gas, carbon monoxide, carbon dioxide, or the like can also be used.

Generally the said high frequency electric power is 13.56MHz and 100-1000W, but it is not limited to this. The application of the high frequency power may be continuous or intermittent (pulse).

As described above, according to the first embodiment, the columnar spacer 9 formed of the dielectric material having the cavity 8 is inserted into and fixed to the upper portion of the external electrode 6 to shoulder at least at the inlet of the PET bottle B. The part is accommodated in the cavity 8 of the spacer 9, and the bottom part side is stored in the main body 4 of the external electrode 6 from the shoulder part of the PET bottle B, so that the PET bottle of the medium gas. Plasma between the external electrode 6 (substantially the inner surface of the PET bottle B) and the grounded internal electrode 20 by supply to (B) and supply to the external electrode 6 of high frequency power. Create As a result, a carbon film having a uniform thickness is provided not only on the inner surface of the bottom portion of the shoulder portion of the PET bottle B, but also on the inner surface of the shoulder portion at the inlet portion of the PET bottle B facing the spacer 9 made of the dielectric material. Can be coated. As a result, an inner surface carbon film-coated PET bottle excellent in blocking property can be produced which prevents the permeation of oxygen from the outside and the permeation of carbon dioxide from the inside (for example, carbonated beverage).

In addition, by forming the spacer 9 with a dielectric material such as plastic that can be injection molded, for example, it is possible to correspond to the shape of the member covering the inlet and shoulder portions of the PET bottle B. For this reason, it can manufacture easily compared with the case where all including these members are comprised with an external electrode like conventionally. Moreover, as compared with the case where all including these members are comprised by the external electrode by the electrically-conductive material like metal conventionally, the whole apparatus can be reduced in weight.

In addition, by forming the spacer 9 with a dielectric material such as plastic or soft ceramic, it is possible to prevent the occurrence of a wound at the place where the PET bottle B is in contact with a complicated entrance portion and a shoulder portion.

In addition, in the above-described first embodiment, the cylindrical spacer 9 made of a dielectric material having the cavity 8 is placed on the shoulder portion from the inlet portion of the PET bottle B to the upper portion of the main body 4 of the external electrode 6. Although inserted and fixed correspondingly, the thin film made of the dielectric material may be extended from the shoulder portion of the PET bottle B to the bottom portion.

(Example 1)

Using the carbon film forming apparatus shown in FIG. 1 described above, the shoulder portion is received from the inlet portion of the PET bottle B in contact with the inner surface thereof in the cavity portion 8 of the spacer 9 made of a dielectric material, and the bottle The bottom side was brought into contact with the inner surface of the external electrode 6 from the shoulder portion of (B), and the carbon film was coated on the inner surface of the PET bottle (B) under the following conditions. In addition, the columnar spacer 9 corresponds to the inlet portion and the shoulder portion of the PET bottle B having a height of about 22 cm accommodated in the external electrode 6 in the external electrode 6 (the position of 11 cm from the top). ).

<Coating condition>

Circumferential spacer 9: It was manufactured from Hotbell (brand name, the product made from Smithkin Co., Ltd.).

Gas injection hole 22 of plug 23: hole diameter 1 mm, one.

Medium: C ₂ H ₂ gas.

Medium gas flow rate: 124 sccm.

Gas pressure in PET bottle B and exhaust pipe 12: 0.3 Torr.

High frequency power supplied to the external electrode 6: 13MHz, 1600W.

(Example 2)

Using the conventional carbon film forming apparatus shown in Fig. 18, the bottom side is brought into contact with the inner surface of the external electrode 201 from the inlet of the PET bottle B having a height of about 22 cm, and the PET bottle B is subjected to the following conditions. ) Carbon coating on the inner surface.

<Coating Condition>

Gas injection hole 206 of the internal electrode 205: hole diameter 1 mm, one.

Medium: C ₂ H ₂ gas.

Gas flow rate of the medium: 58 sccm.

Gas pressure in PET bottle B: 0.16 Torr.

High frequency power supplied to the external electrode 201: 13 MHz, 700 W.

The thickness from the inlet part to the bottom part of the PET bottle which coated the carbon film by Example 1 and Example 2 is measured, and the result is shown in FIG.

From Fig. 2, in Example 1 of the present invention in which a cylindrical spacer 9 made of a hot bell is inserted into an outer electrode 6 corresponding to an inlet portion and a shoulder portion of a PET bottle B, the entire inner surface of the PET bottle B is placed. It can be clearly seen that a uniform carbon film is coated.

On the other hand, in the conventional example 2 which accommodated the bottom part side in contact with the inner surface of the external electrode 201 from the inlet part of PET bottle B, in the inner surface of the bottle part B from the inlet part to the inner surface vicinity of the shoulder part among the inner surfaces of the PET bottle B. It can be seen that the thick carbon film is coated, so that the thickness of the carbon film becomes uneven. In addition, in Example 2, the thickness of the location which is 5 cm in height was not entered because the thickness of the carbon film in the location had peeled thick.

(2nd embodiment)

3 is a cross-sectional view showing the carbon film forming apparatus on the inner surface of the plastic container according to the second embodiment. In addition, in FIG. 3, the same member as FIG. 1 mentioned above attaches | subjects the same code | symbol, and abbreviate | omits description.

In the carbon film forming apparatus of FIG. 3, a conductive member 24 having a ring shape is formed on the upper end surface of the spacer 9 and extends downward from the main edge thereof, and the cylinder is a main body of the external electrode 6. (4) It has a structure provided to coincide with the upper end of the outer electrode 6 so as to be connected to the inner surface. The high frequency power supply 15 also serves as a bias power supply.

Next, the manufacturing method of an inner surface carbon film coating plastic container is demonstrated using the carbon film forming apparatus shown in FIG.

The bottom part of the external electrode main body 4 is opened by taking the external electrode bottom member 5, the disk-shaped insulator 7, the base 3, etc. by the pusher which is not shown in figure. Subsequently, the plastic container, for example, the PET bottle B, is inserted from the bottom side of the open electrode body 4 from the inlet side of the bottle B. Next, the external electrode bottom member 5, the disk-shaped insulator 7, and the base 3 are attached in this order to the bottom side of the external electrode body 4 by a pusher (not shown). Thereby, as shown in FIG. 3, the shoulder part from the inlet part of PET bottle B is accommodated in the cavity part 8 of the cylindrical spacer 9 which consists of dielectric materials, and also the shoulder of the said bottle B is carried out. The bottom side is stored in the external electrode 6 from the portion. At this time, the PET bottle B communicates with the exhaust pipe 12 through its inlet.

Subsequently, gas inside and outside the said exhaust pipe 12 and the PET bottle B is exhausted through the branch exhaust pipe 13 and the exhaust pipe 12 by the exhaust means not shown. The medium gas is supplied to the gas flow passage 21 of the internal electrode 20 through the gas supply pipe 19, and the PET bottle from the gas injection hole 22 of the stopper 23 attached to the bottom of the internal electrode 20. It is made to spray in (B). This medium gas further flows toward the inlet of PET bottle B. Subsequently, the gas supply amount and the gas exhaust amount are balanced, and the inside of the PET bottle B is set to a predetermined gas pressure.

Subsequently, high frequency power is supplied from the high frequency power supply 15 which also serves as a bias to the external electrode 6 through the cable 16, the matching unit 18 and the power supply terminal 17. At this time, plasma is generated around the internal electrode 20. In addition, since the external electrode 6 is electrically connected to the conductive member 24 disposed on the spacer 9 made of a dielectric material, the external grounded exhaust pipe 12 in the vicinity thereof is used as a reference potential. A bias voltage can be applied from the external electrode 6 toward the internal electrode 20, ie toward the generated plasma. By the generation of the plasma and the introduction of the plasma into the external electrode 6, a bias power was applied to the film forming species obtained by dissociating the medium gas into the plasma, and the PET bottle in the bottomed cylindrical external electrode 6 was applied. (B) It is possible to coat a homogeneous carbon film with a uniform thickness on the inner surface.

After the film thickness of the carbon film reaches a predetermined thickness, the supply of the high frequency power from the high frequency power supply 15 is stopped, the supply of the medium gas is stopped, the residual gas is exhausted, and the exhaust of the gas is stopped. Subsequently, nitrogen, a rare gas, or air is introduced into the PET bottle B through the gas flow passage 21 of the internal electrode 20 and the gas injection hole 22 of the stopper 23 through the gas supply pipe 12. Supply. Thereby, the inside and outside of PET bottle B are returned to atmospheric pressure, and the inner surface carbon film coating PET bottle is picked up. Thereafter, the PET bottles are exchanged in the above-described order, and the process moves to the next PET bottle coating operation.

As said medium gas, the thing similar to what was demonstrated in the said 1st Embodiment can be used.

Generally the said high frequency electric power is 13.56 MHz and 100-1000 W, but it is not limited to this. The application of the high frequency power may be continuous or intermittent (pulse).

As described above, according to the second embodiment, the cylindrical spacer 9 made of a dielectric material having the cavity 8 is inserted into and fixed to the upper portion of the external electrode 6, and the conductive member 24 is fixed to the spacer 9. Disposed in connection with the external electrode 6, the shoulder portion is housed in the cavity 8 of the spacer 9 from at least an inlet of the PET bottle B, and the shoulder portion of the PET bottle B The bottom side is stored in the external electrode 6, and the external electrode 6 (substantially the PET bottle is supplied by supplying medium gas into the PET bottle B and supplying the high frequency electric power to the external electrode 6. (B) inner surface] and the grounded internal electrode 20 to generate a plasma. As a result, a carbon film having a uniform thickness is provided not only on the inner surface of the bottom portion of the shoulder portion of the PET bottle B, but also on the inner surface of the shoulder portion at the inlet portion of the PET bottle B facing the spacer 9 made of the dielectric material. It may be coated, and further, a homogeneous carbon film may be coated with a uniform thickness on the entire inner surface including the shoulder part from the inlet of the PET bottle (B). As a result, an inner surface carbon film-coated PET bottle excellent in barrier property which prevents permeation of oxygen from the outside and permeation of carbon dioxide from the inside (for example, carbonated beverage) can be produced.

In addition, by forming the spacer 9 by, for example, a dielectric material such as plastic capable of injection molding, it is possible to correspond to a complicated shape member covering the inlet and shoulder portions of the PET bottle B. For this reason, it can manufacture easily compared with the case where all including these members are comprised with an external electrode like conventionally. Moreover, as compared with the case where all including these members are comprised by the external electrode by the electrically-conductive material like metal conventionally, the whole apparatus can be reduced in weight.

In addition, by forming the spacer 9 with a dielectric material such as plastic or soft ceramic, it is possible to prevent the occurrence of scratches at the location when the complicated entrance portion and the shoulder portion of the PET bottle B come into contact with each other.

In addition, when a bias power is applied using the conductive member 24 connected to the external electrode 6 using the grounded exhaust pipe 12 near the conductive member 24 as a reference potential, the conductive member 24 is applied. And unnecessary plasma are generated between the exhaust pipe 12, that is, in the exhaust pipe 12, and the coating efficiency of the carbon film is lowered. By exposing an inner surface portion of the exhaust pipe 12 near the conductive member 24 and covering a portion of the exhaust pipe 12 above it with an insulating film (not shown), it is possible to prevent generation of the unnecessary plasma. do.

In the second embodiment described above, the cylindrical spacer 9 made of a dielectric material having the cavity 8 is inserted in the upper portion of the external electrode 6 so as to correspond to the shoulder portion from the inlet portion of the PET bottle B. Although fixed, the thin film made of a dielectric material may be extended from the shoulder portion of the PET bottle B to the bottom portion.

(Example 3)

Using the carbon film forming apparatus shown in FIG. 3 described above, the cavity portion 8 of the spacer 9 made of a dielectric material having an annular conductive member 24 attached to the shoulder portion from the inlet portion of the PET bottle B at the upper end thereof. ) And the inner surface of the bottle (B) in contact with the inner surface, and the bottom side from the shoulder portion of the bottle (B) in contact with the inner surface of the external electrode (6), and the carbon film is coated on the inner surface of the bottle (B) under the following conditions do. In addition, the columnar spacer 9 corresponds to the inlet portion and the shoulder portion of the PET bottle B having a height of about 22 cm accommodated in the outer electrode 6 in the outer electrode 6 (the position of 11 cm from the top). Inserted in

<Coating Condition>

Circumferential spacer 9: Hotbell (trade name, product of Smykin Ceramic Co., Ltd.).

Ring-shaped conductive member 24 made of stainless steel.

. Gas injection hole 22 of the stopper 23: hole diameter 1mm, one.

Medium: C ₂ H ₂ gas.

Gas flow rate of the medium: 26 to 394 sccm.

Gas pressure in PET bottle B and exhaust pipe 12: 0.08 to 1 Torr.

High frequency power applied to the external electrode 6: 13.56 MHz, output 100 W (constant).

(Example 4)

In the carbon film forming apparatus shown in FIG. 3 described above, the shoulder portion from the inlet portion of the PET bottle B is formed in the cavity 8 of the spacer 9 made of a dielectric material having no annular conductive member attached to the upper end thereof. The inner surface of the bottle B was brought into contact with the inner surface, and the bottom side of the bottle B was brought into contact with the inner surface of the external electrode 6, and the carbon film was formed on the inner surface of the bottle B under the same conditions as in Example 2. Coating.

In Examples 3 and 4, when the high frequency power of 13.56 MHz and the output 100W were applied to the external electrode 6, and the gas pressure in the PET bottle B and the exhaust pipe 12 was changed to 0.08-1 Torr, the internal electrode 20 was carried out. Bias voltage is measured, and the results are shown in FIGS. 4 (Example 3) and 5 (Example 4).

4 and 5, in Example 3 according to the second embodiment, when a high frequency power of 13.56 MHz and an output of 100 W is applied to the external electrode 6, a bias voltage of -100 V to -300 V is internal due to a change in pressure. It can be clearly seen that it is applied to the electrode 20. On the other hand, in Example 4 without the conductive member, it can be seen that the bias voltage can hardly be applied toward the internal electrode 20 even when the pressure is changed by applying the same high frequency power. This is because, in Example 3, the conductive member 24 extending from the external electrode 6 is attached to the upper end of the spacer 9 so as to face the grounded exhaust pipe 12 that is opposite to the conductive member 24, and to the reference potential. This is because it can be used as.

(Example 5)

Using the carbon film forming apparatus shown in FIG. 3 described above, the cavity portion 8 of the spacer 9 made of a dielectric material having an annular conductive member 24 attached to the top of the shoulder portion from the inlet portion of the PET bottle B. ) And the inner surface of the bottle (B) in contact with the inner surface, and the bottom side of the bottle (B) in contact with the inner surface of the external electrode (6) for storage, coating the carbon film on the inner surface of the bottle (B) under the following conditions did. In addition, the columnar spacer 9 corresponds to the inlet portion and the shoulder portion of the PET bottle B having a height of about 22 cm accommodated in the outer electrode 6 in the outer electrode 6 (the position of 11 cm from the top). Inserted in

<Coating condition>

Circumferential spacer 9: Hotbell (trade name, product of Smykin Ceramic Co., Ltd.).

Ring-shaped conductive member 24 made of stainless steel.

Gas injection hole 22 of plug 23: hole diameter 1 mm, one.

Medium: C ₂ H ₂ gas.

Medium gas flow rate: 80 sccm.

Gas pressure in PET bottle B and exhaust pipe 12: 0.2 Torr (constant).

High frequency power applied to the external electrode 6: 13.56 MHz, output 100-500 W.

(Example 6)

In the carbon film forming apparatus shown in FIG. 3 described above, the cavity portion 8 of the spacer 9 made of a dielectric material having no shoulder-shaped conductive member attached to the shoulder portion from the inlet portion of the PET bottle B. The inner surface of the PET bottle B was kept under the same conditions as those of the third embodiment, and the inner surface of the bottle B was brought into contact with the inner surface thereof, and the bottom side was brought into contact with the inner surface of the external electrode 6 from the shoulder portion of the bottle B. Was coated with a carbon film.

In Examples 5 and 6, when the high frequency electric power of 13.56 MHz and the output 100-500 W was applied to the external electrode 6, and the gas pressure in PET bottle B and the exhaust pipe 12 was made constant to 0.2 Torr, the internal electrode. The bias voltage for (20) was measured, and the results are shown in Figs. 6 (Example 5) and 7 (Example 6).

6 and 7, in Example 5 according to the second embodiment, the gas pressure is constant, and the high frequency power of 13.56 MHz is applied to the external electrode 14 by varying its output so that from -100V to -500V. It can be clearly seen that the bias voltage is applied to the internal electrode 20. On the other hand, in Example 6 without the conductive member, it can be seen that the bias voltage can hardly be applied toward the internal electrode 20 even when the gas pressure is constant and the output is applied at a high frequency. This is because in Example 5, the conductive member 24 extending from the external electrode 14 is attached to the upper end of the spacer 9 so as to face the grounded exhaust pipe 12 that is opposite to the conductive member 24 and to the reference potential. This is because it can be used as.

According to Examples 3 and 5 according to the second embodiment, the plasma generated in the PET bottle B can be introduced into the external electrode 6 by the above-described bias voltage, so that the inner surface of the PET bottle B has a uniform thickness. The carbon film can be coated.

(Third 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 third embodiment, and FIG. 9 is an enlarged cross-sectional view of the main portion of FIG. 8.

The cylindrical support members 42 having the flanges 41a and 41b at the upper and lower ends are mounted on the annular base 43. The outer electrode main body 44 made of a cylindrical metal is disposed in the support member 42. The metal outer electrode bottom member 45 having a disk shape is detachably attached to the bottom of the external electrode 44. For example, a bottomed cylindrical external electrode having a space that can be installed in a plastic container (for example, a PET bottle) B in which a carbon film is formed by the external electrode body 44 and the external electrode bottom member 45. 46 is comprised. In addition, a disc shaped insulator 47 is disposed between the base 43 and the external electrode bottom member 45.

The external electrode bottom member 45, the disc-shaped insulator 47, and the base 43 are integrally moved up and down with respect to the external electrode main body 44 by a pusher (not shown). The bottom part of the main body 44 is opened and closed.

The columnar spacer 49 made of a dielectric material is inserted above the main body 44 in the external electrode 46. The spacer 49 has a cavity portion 48 having a shape in which a circumference and a truncated cone corresponding to the inlet portion and the shoulder portion of the PET bottle B inserted therein are combined. The spacer 49 is fixed by screws (not shown) screwed from the annular insulating member described later mounted thereon. The conductive member 50 is provided on the upper end face of the spacer 49 in planar correspondence with the upper end of the outer electrode 46 in the outer electrode 46. The conductive member 50 has a ring shape and has a shape in which the cylinder is extended downward from the main edge thereof. Thus, in the structure which inserted and fixed the columnar spacer 49 and the electrically-conductive member 50 in the upper part of the said main body 44 in the said external electrode 46, PET bottle at the bottom side of the said external electrode 46. When (B) is inserted, the inlet portion and the shoulder portion of the outer circumference of the PET bottle (B) are accommodated in the cavity portion 55 of the spacer 56, and the outer circumference of the PET bottle (B) is inserted into the outer electrode 46. It is stored.

As the dielectric material constituting the spacer 49, the same materials as those described in the first embodiment can be used.

The annular insulating member 51 is mounted on the surface of the external electrode 46 such that its annular insulating member 51 surface coincides with the upper flange 41a of the cylindrical supporting member 42. Gas exhaust pipes 53 having flanges 52a and 52b above and below are mounted on the upper flange 41a of the support member 42 and the surfaces of the annular insulating member 51. This exhaust pipe 53 is grounded. The gas exhaust pipe 53 is attached to the support member 42 by screwing a screw (not shown) from the lower flange 52b of the exhaust pipe 53 to the upper flange 41a of the support member 42. It is fixed. In addition, the exhaust pipe 53 screws the screw (not shown) to the main body 44 of the external electrode 46 by passing through the annular insulating portion 51 from the lower flange 53b of the exhaust pipe 53. This is fixed to the annular insulating member 51 and the external electrode 46. The annular insulating member 51 is also fixed to the external electrode 46 by the screw. In addition, the exhaust pipe 53, the annular insulating member 51, and the external electrode 46 are fixed to each other so that the exhaust pipe 53 and the external electrode 46 are not electrically connected by screws. It becomes the structure that becomes. One end of the branch gas exhaust pipe 54 is connected to the side wall of the gas exhaust pipe 53. The other end of this branch gas exhaust pipe 54 is provided with an exhaust device such as a vacuum pump (not shown).

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

A grounded lid structure 60 having an insulating ring 59 at its center is provided on the upper flange 52a of the exhaust pipe 53. The housing 61 is provided on the cover structure 60.

A gas supply pipe 62 serving as a terminal having a high high frequency power penetrates through the insulating ring 59 of the lid structure 60 in the housing 61 and passes through the gas exhaust pipe 53 and the spacer 49. It is inserted inside. The upper end of the gas supply pipe 62 is connected to the lower end of the gas introduction pipe 63 inserted through the housing 61 from the outside via an insulating coupling 64.

The ground shield pipe 66 having the flange pipe 65 at its upper end is disposed so as to cover a portion of the gas supply pipe 62 positioned in the gas exhaust pipe 53 and the spacer 49. In addition, the ground shield pipe 66 is located in the spacer 49 and in the gas exhaust pipe 53 near the spacer 49. An upper end of the flange tube 65 is connected to the rear surface of the lid structure 60. That is, the ground shield pipe 66 is connected to the lid structure 60 grounded through the flange pipe 65.

The inner electrode 67 is disposed in the outer electrode 46 and the spacer 49 (the space where the PET bottle B is inserted) over its entire length in the longitudinal direction. The upper end of the internal electrode 67 is attached to the lower end of the gas supply pipe 62 positioned on the spacer 49 side with a detachable material. The internal electrode 67 has a gas flow passage 68 formed on a central axis. The stopper 70 is attached to the bottom of the internal electrode 67 with a detachable material. The stopper 70 is provided with a gas injection hole 68 for injecting a medium gas.

In addition, the gas injection hole may be opened to communicate with the gas flow path 68 on the lower sidewall of the internal electrode (67). In this case, the gas injection hole is preferably opened in the side region in the range of up to 25% of the length inserted into the PET bottle B at the bottom of the internal electrode 67.

The diameter of the inner electrode 67 is equal to or smaller than the diameter of the metal cap of the bottle B, and the length is a length that can be inserted over almost the entire length of the PET bottle B. FIG. The length is such that the ratio of the PET bottle B to the full length is about {1-D / (2L)}. Where D is the inside diameter of PET bottle, L is the full length of PET bottle, and L> (D / 2).

The internal electrode 67 is made of a metal material having heat resistance such as tungsten or stainless steel, but may be made of aluminum. In addition, when the surface of the internal electrode 20 is smooth, there is a possibility that the carbon film deposited on the surface of the internal electrode 20 may be easily peeled off. For this reason, it is preferable that the surface of the internal electrode 20 is subjected to sand blasting in advance to increase the surface roughness, thereby making it difficult to peel off the carbon film deposited on the surface.

The high high frequency power supply 71 is connected to the side surface of the said gas supply pipe 62 which also serves as a terminal of a high high frequency electric power through the cable 72 and the power supply terminal 73. The matcher 74 is attached to the cable 72 between the high high frequency power supply 71 and the power supply terminal 73.

The insulating film 75 is formed on the inner surface of the exhaust pipe 53 facing the ground shield pipe 66. This insulating film 75 is made from a fluorine resin such as polytetrafluoroethylene.

Next, a method of manufacturing an inner surface carbon film-coated plastic container using the apparatus shown in FIGS. 8 and 9 will be described.

The bottom part of the external electrode main body 44 is opened by removing the external electrode bottom member 45, the disc shaped insulator 47, and the base 43 by a pusher (not shown). Subsequently, a plastic container such as a PET bottle B is inserted from the inlet side of the bottle B on the bottom side of the opened external electrode body 4. Subsequently, the external electrode bottom member 45, the disk-shaped insulator 47, and the base 43 are attached to the bottom side of the external electrode body 44 by a pusher (not shown) in this order. Thereby, as shown in FIG. 8, the shoulder part from the inlet part of PET bottle B is the bottom part from the shoulder part of the said bottle B in the cavity 48 of the columnar spacer 49 which consists of dielectric material. The side is accommodated in the external electrode 46. At this time, the PET bottle (B) is communicated to the exhaust pipe (53) through its inlet.

Subsequently, the gas in and out of the said exhaust pipe 53 and the said PET bottle B is exhausted through the branch exhaust pipe 54 and the exhaust pipe 53 by the exhaust means not shown. Subsequently, the medium gas is supplied to the gas flow passage 68 of the internal electrode 67 through the gas introduction pipe 63 and the gas supply pipe 62. The supplied medium gas is injected into the PET bottle B from the gas injection hole 69 of the stopper 70 attached to the bottom of the internal electrode 67. This medium gas further flows toward the inlet of PET bottle B. Next, the gas supply amount and the gas exhaust amount are balanced, and the inside of the PET bottle B is set to a predetermined gas pressure.

Subsequently, the bias power is supplied from the bias power supply 55 to the external electrode 46 through the cable 56, the matching unit 59, and the feed terminal 57. Thereafter, or at the same time, high frequency power from the high frequency power supply 71 is supplied to the gas supply pipe 62 through the cable 72, the matching device 74, and the power supply terminal 73, and the gas supply pipe ( High frequency power is supplied to the internal electrode 67 through 62. At this time, plasma is generated around the internal electrode 67. The external electrode 46 is also electrically connected to a conductive member 50 disposed on a spacer 49 made of a dielectric material. For this reason, a bias voltage can be applied from the external electrode 46 toward the internal electrode 87, that is, toward the generated plasma, with the grounded exhaust pipe 63 near the conductive member 50 as the reference potential. .

As a result, a) using a high frequency power, a high electron density is obtained in comparison with the high frequency power under a particularly low gas pressure condition, so that the collision frequency with the medium gas can be increased to increase the film-forming species density. b) Since the potential difference with the plasma potential can be changed 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, the ion melter incident on the inner surface of the PET bottle (B) can be controlled by using together with the adjustment of the electric potential difference. By the generation of the plasma and the introduction of the plasma to the external electrode 46 by the application of the bias voltage to the internal electrode 67, the external film having the bias power applied to the film forming species obtained when dissociating the medium gas into the plasma. On the inner surface of the PET bottle B in the electrode 46, a homogeneous carbon film with a uniform thickness can be coated on the highway.

After the thickness of the carbon film reaches a predetermined film thickness, the bias power and the high frequency power supply from the bias power supply 55 and the high frequency power supply 71 are stopped, and the supply of the medium gas is stopped and the residual gas is stopped. Is exhausted to stop the gas exhaust. Subsequently, nitrogen, a rare gas, or air is removed from the gas introduction pipe 63 and the gas injection hole 69 of the gas supply pipe 62, the gas flow path 68 of the internal electrode 67, and the stopper 70. It supplies into PET bottle B through this, and returns the inside and outside of this PET bottle B to atmospheric pressure. Next, the inner surface carbon film coated PET bottle is picked up. Thereafter, the PET bottle B is replaced in accordance with the above-described procedure, and the process moves to the next PET bottle coating operation.

As said medium gas, the thing similar to what was demonstrated in the said 1st Embodiment can be used.

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

The bias power is generally 13.56 MHz and 100 to 1000 W, but is not limited thereto. In addition, the application of the bias power may be continuous or intermittent (pulse).

As described above, according to the third embodiment, the cylindrical spacer 49 made of the dielectric material having the cavity 48 is inserted and fixed on the upper portion of the external electrode 46 and the conductive member 50 is fixed to the spacer 49. Disposed in connection with the external electrode 46, the shoulder portion is housed in the cavity 48 of the spacer 49 from at least an inlet portion of the PET bottle B, and the shoulder portion of the PET bottle B From the bottom side to the external electrode 46 to supply medium gas to the PET bottle B, apply bias power to the external electrode 46, and supply high-frequency power to the internal electrode 87. The plasma is generated between the inner electrode 87 and the outer electrode 46 (substantially the inner surface of the PET bottle B). Thereby, a carbon film having a uniform thickness is formed not only on the inner surface of the bottom portion from the shoulder portion of the PET bottle B, but also on the inner surface of the shoulder portion from the inlet portion of the PET bottle B facing the spacer 49 made of the dielectric material. Can be coated. In addition, it is possible to coat a homogeneous carbon film with a uniform thickness on the entire inner surface including the shoulder portion from the inlet of the PET bottle (B). In particular, by supplying high frequency power to the internal electrode 87, the carbon film can be highway coated on the entire inner surface of the PET bottle B as compared with the above-described second embodiment. As a result, it is possible to mass-produce an inner surface carbon film-coated PET bottle excellent in barrier properties which prevents the permeation of oxygen from outside and the permeation of carbon dioxide from the inside (for example, carbonated beverage).

In addition, by forming the spacer 49 by a dielectric material such as plastic that can be injection-molded, for example, it is possible to correspond to a complicated shaped member covering around the inlet and shoulder portions of the PET bottle B. For this reason, it can manufacture easily compared with the case where all including these members are comprised with an external electrode like conventionally. Moreover, as compared with the case where all including these members are comprised by the external electrode by the electrically-conductive material like metal conventionally, the whole apparatus can be reduced in weight.

In addition, by forming the spacer 49 by a dielectric material such as plastic or soft ceramic, it is possible to prevent the occurrence of scratches at the location when the complicated inlet portion and the shoulder portion of the PET bottle B come into contact with each other.

In addition, between the conductive member 50 and the exhaust pipe 53, that is, within the exhaust pipe 53, the conductive member 50 connected to the external electrode 46 is grounded near the conductive member 50. By applying the bias power using the exhaust pipe 53 as the reference potential, unnecessary plasma is generated between the conductive member 50 and the exhaust pipe 53, that is, within the exhaust pipe 53. For this reason, the coating efficiency of a carbon film falls. The generation of such unnecessary plasma can be prevented by exposing the inner surface portion of the exhaust pipe 60 near the conductive member 50 and covering the upper exhaust pipe 63 portion with the insulating film 73.

In addition, an unnecessary plasma is also generated between the gas supply pipe 62 to which high high frequency power is applied and the grounded exhaust pipe 53, that is, in the exhaust pipe 60, to reduce the coating efficiency of the carbon film. The generation of such unnecessary plasma can be prevented by arranging the ground shield pipe 66 grounded around the gas supply pipe 62.

In addition, in the above-described third embodiment, the cylindrical spacer 49 made of a dielectric material having the cavity portion 48 is inserted in the upper portion of the external electrode 46 so as to correspond to the shoulder portion from the inlet portion of the PET bottle B. Although fixed, the thin film made of the dielectric material may be extended further from the shoulder portion of the PET bottle B over the bottom portion.

(Example 7)

Using the carbon film forming apparatus shown in FIG. 8 and FIG. 9 described above, the PET bottle B is made of a spacer 49 made of a dielectric material having a shoulder portion from an inlet portion thereof and an annular conductive member 50 attached to an upper end thereof. The inner surface of the cavity 48 in contact with the inner surface thereof was accommodated. Further, the bottom side was brought into contact with the inner surface of the external electrode 46 from the shoulder portion of the bottle B. In this state, a carbon film was coated on the inner surface of the PET bottle (B) under the following conditions. In addition, the columnar spacer 49 corresponds to the inlet portion and the shoulder portion of the PET bottle B having a height of about 22 cm accommodated in the outer electrode 46 in the outer electrode 46 (the position of 11 cm from the top). Was inserted in.

<Coating condition>

Circumferential spacer 49: Hotbell [trade name, the product made by Smithkin Co., Ltd.].

Ring-shaped conductive member 50 made of stainless steel.

Gas injection hole 69 of the stopper 70: hole diameter 1mm, one,

Medium: C ₂ H ₂ gas.

Gas flow rate of the medium: 40 to 80 sccm.

Gas pressure in PET bottle B and exhaust pipe 53: 0.08 to 0.2 Torr.

High high frequency power supplied to the internal electrode 67: 100 MHz, 250 W.

High frequency power applied to the external electrode 46: 13.56 MHz, output 250 W.

In Example 7, bias was applied to the internal electrode 67 when a high frequency power of 13.56 MHz and an output of 250 W were applied to the external electrode 46 and the gas pressure in the PET bottle B and the exhaust pipe 53 was 0.2 Torr. The voltage was measured. The result is shown in FIG.

10, in Example 7, according to the third embodiment, at a pressure of 0.2 Torr, a bias voltage of about 1450 V is applied to supply high frequency power of 250 W as in Example 5 (shown in FIG. 6) according to the second embodiment described above. It can be clearly seen that the same bias voltage can be applied.

According to this example 7, high-frequency power is supplied to the internal electrode 67 to generate a high-density plasma in the PET bottle B, and the plasma is introduced into the external electrode 54 by the above-described bias voltage. It is possible to coat the carbon film of uniform thickness on the inner surface of the PET bottle (B) by highway.

(4th embodiment)

11 is a cross-sectional view showing the film forming apparatus on the inner surface of the plastic container according to the fourth embodiment.

The cylindrical electromagnetic shield member 102 having the upper and lower flanges 101a and 101b is mounted on the annular lower shield member 103 and electrically connected to it so as to prevent high frequency leakage from the device. . The outer electrode main body 104 made of cylindrical metal is disposed in the electromagnetic shield member 102 so as to be positioned below the upper flange 101a. The disc-shaped external electrode bottom member 105 made of metal is detachably attached to the bottom of the external electrode 104. For example, a bottomed cylindrical external electrode having a space of a size capable of installing a plastic container (for example, a PET bottle) B for forming a carbon film by the external electrode body 104 and the external electrode bottom member 105. 106 is configured. In addition, a disc shaped insulator 107 is disposed between the lower shield member 103 and the external electrode bottom member 105.

In addition, the external electrode bottom member 105, the disc shaped insulator 107, and the lower shield member 103 are vertically moved up and down with respect to the external electrode body 104 by a pusher (not shown). The bottom part of the external electrode main body 104 is opened and closed.

The cylindrical spacer 109 made of a dielectric material is inserted above the main body 104 in the external electrode 106. This cylindrical spacer 109 has a cavity 108 having a shape in which a circumference and a truncated cone corresponding to the inlet portion and the shoulder portion of the plastic container (for example, a PET bottle) B inserted therein are combined. The spacer 109 is fixed by screws (not shown) screwed from the annular insulating member described later mounted thereon. Thus, when the PET bottle B is inserted from the bottom side of the external electrode 106 by inserting and fixing the columnar spacer 109 on the upper part of the main body 104 in the external electrode 106, the PET bottle (B) A shoulder portion of the outer circumference contacts or approaches the inner surface of the cavity 108 of the spacer 109, and an outer circumference of another PET bottle B contacts or approaches the inner surface of the external electrode 106. do.

As a dielectric material which comprises the said spacer 109, the thing similar to what was demonstrated in the said 1st Embodiment is mentioned.

The annular insulating member 110 is mounted on the surface of the external electrode 106 such that the surface of the annular insulating member 110 coincides with the upper flange 101a of the cylindrical electromagnetic shield member 102. The spacer 109 is inserted into and fixed in the external electrode 106 by screwing a screw (not shown) from the annular insulating member 110 to the spacer 109. The lower surface of the said annular insulating member 110 can also be made to correspond with the upper surface of the entrance part of PET bottle B. As shown in FIG. However, it is more preferable to make it thicker to the shoulder part side than the inlet part of PET bottle (B). This is to suppress the plasma generated inside the PET bottle B, prevent the film from adhering to the inner surface of the inlet portion of the PET bottle B, and improve the appearance.

Gas exhaust pipes 112 having flanges 111a and 111b above and below are mounted on the upper flange 101a of the electromagnetic shield member 102 and the surfaces of the annular insulating member 110. The gas exhaust pipe 112 screws the screw (not shown) from the lower flange 111b of the exhaust pipe 112 to the upper flange 101a of the electromagnetic shield member 102. 102). In addition, the exhaust pipe 112 screws through the annular insulating member 110 from the lower flange 111b of the exhaust pipe 112 to the main body 104 of the external electrode 106. This is fixed to the annular insulating member 110 and the external electrode 106. The annular insulating member 110 is also fixed to the external electrode 106 by screwing the screw. The exhaust pipe 112, the annular insulating member 110, and the external electrode 106 are fixed to each other so that the exhaust pipe 112 and the external electrode 106 are not electrically connected by screws. It becomes the structure that becomes. The branched gas exhaust pipe 113 has one end connected to the side wall of the gas exhaust pipe 112. The other end of the branch gas exhaust pipe 113 is provided with an exhaust device such as a vacuum pump (not shown).

For example, the bias power source 114 for applying a high frequency power of 13.56 MHz as the bias power is connected to the external electrode 106 through the power supply unit 116 using a coaxial cable 115 and an N type receptacle (not shown). Is connected to. The matcher 117 is attached to the coaxial cable 115. In addition, the lower flange 111b of the exhaust pipe 112 is grounded by an outer shield (not shown) of the coaxial cable 115. In addition, all members, such as the electromagnetic shield member 102, which are electrically connected to the lower flange 111b, are all grounded.

The lid structure 119 is hermetically fixed to the upper flange 111a of the gas exhaust pipe 112. The cover structure 119 has an insulating ring 118 at the center and is grounded by electrical connection with the lower flange 111b. The housing 120 is attached on the cover structure 119.

A gas supply pipe 121 serving as a terminal having a high high frequency power penetrates through the insulating ring 118 of the cover structure 119 in the housing 120, and passes through the gas exhaust pipe 112 to the spacer 109. It is inserted to the inside. The upper end of the gas supply pipe 121 is connected to the lower end of the gas introduction pipe 122 inserted through the housing 120 from the outside through an insulating coupling 123.

The ground shield pipe 124 having the flange portion 125 at its upper end is disposed so as to cover the gas supply pipe 121 located in the gas exhaust pipe 112 and the spacer 109. The ground shield tube 124 is fixed and grounded by screwing the upper flange portion 125 to the lid structure 119. In addition, the ground shield tube 124 is located in the spacer 109 and in the gas exhaust pipe 112 near the spacer 109.

The internal electrode 126 is disposed in the external electrode 106 and the spacer 109 (the space into which the PET bottle B is inserted) over the entire length in the longitudinal direction thereof. The upper end of the internal electrode 126 is attached to the lower end of the gas supply pipe 121 positioned on the spacer 109 side with a detachable material. The internal flow path 127 is formed on the central axis of the internal electrode 126.

In addition, a gas injection hole may be opened to communicate with the gas flow path 127 on the lower sidewall of the internal electrode 126. In this case, the gas injection hole is preferably opened in the side region in the range of up to 25% of the length inserted into the PET bottle B at the bottom of the internal electrode 126.

The diameter of the internal electrode 126 is equal to or smaller than the diameter of the metal stopper of the bottle B, and the length is a length that can be inserted to almost the entire length of the PET bottle B in the longitudinal direction. The length is set so that the ratio with respect to the full length of PET bottle B will be about {1-D / (2L)}. Where D is the inner diameter of the PET bottle, L is the total length of the PET bottle, and L> (D / 2).

Although the internal electrode 126 can be made of various metal materials, in consideration of the effect of the skin effect on high frequency transmission, the surface is preferably a material having high electrical conductivity and stable material such as aluminum or gold. However, considering the cost, it is preferable to manufacture the whole from aluminum. In addition, there is a possibility that the surface of the internal electrode 126 is smoothed in the middle, and the carbon film deposited on the surface of the internal electrode 126 may be easily peeled off. Therefore, by sandblasting the surface of the internal electrode 126 in advance, it is preferable to increase the surface roughness to make it difficult to peel off the carbon film deposited on the surface. On the contrary, there is also a method of making the surface very smooth and blowing or scattering the deposited carbon film every time the coating treatment is performed.

A high high frequency power supply 128 for supplying high high frequency power is connected to the gas supply pipe 121 through a coaxial cable 129 and a power feeding unit 130. The matcher 131 is attached to the coaxial cable 129. The power supply unit 130 is installed in the housing 120 using an N (type) receptacle (not shown). The outer shield of the coaxial cable 129 is also connected to the housing 120 through an outer conductor (not shown) of the N-type receptacle, and the ground of the high frequency power supply 128 and the bias power supply 114 is And all have the ground potential of the same potential.

In the above-described carbon film forming apparatus, the high frequency and bias high frequency applied by the bias power source 114 and the high frequency power source 128 include a lower shield member 103, a cylindrical electromagnetic shield member 102, The exhaust pipe 112, the lid structure 119, and the housing 120 are shielded electronically in the apparatus and are not discharged into the space.

Next, the manufacturing method of an inner surface carbon film coating plastic container is demonstrated using the film forming apparatus shown in FIG.

The bottom part of the external electrode main body 104 is opened by removing the external electrode bottom member 105, the disk-shaped insulator 107, and the lower shield member 103 by a pusher (not shown). Subsequently, a plastic container such as a PET bottle B is inserted from the bottom side of the opened external electrode body 104 from the inlet side of the bottle B. Subsequently, the external electrode bottom member 105, the disk-shaped insulator 107, and the lower shield member 103 are attached in this order to the bottom side of the external electrode body 104 by a pusher (not shown). Thereby, as shown in FIG. 11, the shoulder part is received from the inlet part of PET bottle B in the cavity 108 of the cylindrical spacer 109 made of a dielectric material, in contact with or close to its inner surface, and furthermore, The bottom side of the shoulder portion (B) is brought into contact with or close to the inner surface of the external electrode 106. At this time, the PET bottle (B) is in communication with the exhaust pipe 112 through its inlet.

Subsequently, the gas inside and outside the said exhaust pipe 112 and the PET bottle B is exhausted through the branch exhaust pipe 113 and the exhaust pipe 112 by the exhaust means not shown. The medium gas is supplied from the gas introduction pipe 122 to the gas flow path 126 of the internal electrode 125 through the gas supply pipe 121 to be injected into the PET bottle B. This medium gas further flows toward the inlet of PET bottle B. Subsequently, the gas supply amount and the gas exhaust amount are balanced to set the inside of the PET bottle B to a predetermined gas pressure.

Subsequently, the bias power is applied from the bias power supply 114 to the external electrode 106 through the cable 115, the matching unit 117, and the power supply unit 116. Thereafter, or at the same time, high high frequency power from the high frequency power supply 128 is supplied to the gas supply pipe 121 through the cable 129, the matching unit 131, and the power supply unit 130, and furthermore, The high frequency power is supplied to the internal electrode 126 through the gas supply pipe 121. As a result, plasma is generated around the internal electrode 126.

In this case, the ground shield pipe 124 is disposed on the outer circumference of the gas supply pipe 121 so as to be located in the spacer 109, the annular insulating member 110, and the gas exhaust pipe 112, and the flange portion 125. Grounded through For this reason, a bias voltage can be applied from the external electrode 106 toward the generated plasma using the ground shield tube 124 as a reference potential.

In addition, the high frequency electric field applied to the gas supply pipe 121 is shielded by arranging the ground shield pipe 124 on the outer circumference of the gas supply pipe 121. This makes it possible to prevent the high frequency electric field from being applied to the exhaust pipe 112.

In addition, the high frequency electric field applied to the gas supply pipe 121 and the internal electrode 126 is near the inlet of the PET bottle B by inserting the ground shield pipe 124 into the inside of the PET bottle B. In the part is shielded. For this reason, it is possible to prevent the high frequency electric field from being applied to the space of the inlet of the PET bottle B. Above, when the lower surface of the annular insulating member 110 is set at a height between the upper end of the inlet portion of the PET bottle B and the shoulder portion, the bias voltage applied to the external electrode 106 is applied to the PET bottle B. Application to the space of the inlet can also be prevented.

As a result, the coating speed and film quality of the carbon film on the inner surface of PET bottle B can be improved by the following effects.

a) When high frequency power is used, since a high electron density is obtained compared with high frequency power especially in a low gas pressure condition, the frequency of collision with a medium gas can increase and a film-forming species density can be made high.

b) Since the potential difference with the plasma potential can be changed 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, the ion melter incident on the inner surface of the PET bottle (B) can be controlled by using together with the adjustment of the electric potential difference.

In addition, the following effects are obtained.

d) The high frequency electric field applied to the gas supply pipe 121 is shielded by arranging the ground shield pipe 124 on the outer circumference of the gas supply pipe 121. This makes it possible to prevent the high frequency electric field from being applied to the exhaust pipe 112. As a result, the plasma by the high frequency electric field can be prevented from being strongly generated near the inlet portion of the PET bottle B. Plasma generated inside the PET bottle B because the high frequency power can reach the internal electrode 126 and improve the power transfer efficiency without being consumed by the plasma generated near the inlet of the PET bottle B. Can increase the density.

e) The coating speed of the shoulder portion of the PET bottle B which tends to become thick due to concentration of the electric field can be controlled by adjusting the thickness in the inner diameter direction of the spacer 109 and the length of the ground shield tube 124. For this reason, the coating speed and film | membrane quality of the carbon film in PET bottle B inner surface can be improved.

By the generation of such plasma, a homogeneous carbon film can be coated on the inner surface of the PET bottle B with a uniform thickness, and a high quality inner surface carbon film coated PET bottle can be produced.

After the predetermined film thickness is formed, the supply of the bias power and the high frequency power from the bias power supply 114 and the high frequency power supply 128 are stopped, the supply of the medium gas is stopped, and the residual gas is exhausted. Stop the exhaust of gas. Subsequently, nitrogen, rare gas, or air is supplied from the gas introduction pipe 122 into the PET bottle B through the gas flow passage 127 of the internal electrode 126 through the gas supply pipe 121, and the PET bottle is supplied. (B) Return the inside and outside to atmospheric pressure. Thereafter, the PET bottle B is replaced in the above-described order, and the process moves to the next PET bottle coating operation.

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

Although the said high frequency power is generally defined as 30-300 MHz, it is not limited to this. The application of these powers may be continuous or intermittent (pulse).

The bias power is generally 13.56 MHz, and a range of 50 kHz to 20 MHz and 100 to 1000 W is used, but the present invention is not limited thereto. In addition, the application of the bias power may be continuous or intermittent (pulse).

As described above, according to the fourth embodiment, the grounded ground shield pipe 124 is disposed on the outer circumference of the gas supply pipe 121 so as to be located in the spacer 109 and in the gas exhaust pipe 112 near the spacer 109. At least an inlet portion (B) of the shoulder unit is accommodated in the cavity 108 of the spacer 109, and a bottom side side of the PET bottle B is brought into contact with the outer electrode 106 to be housed. Supplying the medium gas from the gas supply pipe 121 to the PET bottle B through the injection hole of the internal electrode 126 serving as the injection pipe, applying the bias power to the external electrode 106, and applying an internal electrode of high high frequency power. The plasma is generated between the inner electrode 126 and the outer electrode 106 (substantially the inner surface of the PET bottle B) by supply to the 126. By generating the plasma, a carbon film having a uniform thickness can be coated on the inner surface of the PET bottle B. In addition, by applying a bias voltage from the outer electrode 106 toward the inner electrode 126, i.e., toward the generated plasma, the inner surface including the shoulder portion from the inlet of the PET bottle B is homogeneous with a uniform thickness. One carbon film can be coated. In particular, by supplying a high frequency power to the internal electrode 126, it is possible to coat the carbon film on the entire inner surface of the PET bottle (B). As a result, it is possible to mass-produce an inner surface carbon film-coated PET bottle excellent in barrier properties that prevents permeation of oxygen from the outside and permeation of carbon dioxide from the inside (for example, carbonated beverages).

In addition, an unnecessary plasma is generated between the gas supply pipe 121 to which high frequency power is applied and the grounded exhaust pipe 112, that is, in the exhaust pipe 112, and the coating efficiency of the carbon film is lowered. By arranging the grounded ground shield pipe 124 around the gas supply pipe 121, generation of the unnecessary plasma can be prevented.

Moreover, it is preferable that a blocking film does not adhere to the inner surface part of the inlet part in the external appearance of PET bottle (B). Plasma generation of this part can be suppressed by inserting the said ground shield pipe 124 inward from the inlet part of PET bottle B. As shown in FIG. Moreover, application of the bias electric field to the inlet part of PET bottle B can be prevented by arrange | positioning the annular insulating member 110 between the shoulder part from the upper end of the inlet part of PET bottle B. By these two effects, a barrier film is not adhered to the inlet part of PET bottle B, and an inner carbon film coated PET bottle with high commodity value can be obtained. In addition, since the PET bottle B is close to the inner wall of the outer electrode 106 by several millimeters or less, no plasma is generated in the cavity between the outer wall of the PET bottle B and the inner wall of the outer electrode 106. It is not coated on the outer wall of (B).

In addition, by forming the spacer 109 with a dielectric material such as plastic that is capable of injection molding, for example, it is possible to correspond to a complicated shaped member covering around the inlet and shoulder portions of the PET bottle B. For this reason, it can manufacture easily compared with the case where all including these members are comprised with an external electrode like conventionally. Moreover, as compared with the case where all including these members are comprised by the external electrode by the electrically-conductive material like metal conventionally, the whole apparatus can be reduced in weight. This is an important advantage when adopting a rotary type (rotary type) for a high speed continuous coating apparatus.

In addition, in the above-described fourth embodiment, the cylindrical spacer 109 made of a dielectric material having the cavity portion 108 is inserted in the upper portion of the external electrode 106 so as to correspond to the shoulder portion from the inlet portion of the PET bottle B, By fixing, the thin film made of the dielectric material may be extended from the shoulder portion of the PET bottle B to the bottom portion.

In addition, the ground shield pipe 124 is not limited to the shape which positions the lower end in the vicinity of the entrance part of PET bottle B as shown in FIG. For example, as shown in FIG. 12, the lower end of the ground shield tube 124 may be positioned near the center of the trunk portion of the PET bottle B, and the length of the internal electrode 126 may be effectively shortened. By doing in this way, unnecessary plasma which arises in the vicinity of the inlet part of PET bottle B, and in the exhaust pipe 112 can be suppressed. For this reason, the high frequency electric power supplied to an internal electrode can be consumed by the effective plasma in PET bottle B. FIG. Therefore, the coating speed can be improved. In addition, the bias can be effectively applied to the plasma in the PET bottle B, thereby improving the coating quality.

(Example 8)

Using the carbon film forming apparatus shown in FIG. 11 described above, the shoulder portion is received from the inlet portion of the PET bottle B in contact with or close to its inner surface in the cavity portion 108 of the spacer 109 made of a dielectric material, The bottom side of the bottle B was placed in contact with or close to the inner surface of the external electrode 106. The grounded ground shield pipe 124 is disposed on the outer circumference of the gas supply pipe 121 so as to be located in the spacer 109 and in the gas exhaust pipe 112 near the spacer 109, and the inner surface of the PET bottle B is provided under the following conditions. Was coated with a carbon film. In addition, the columnar spacer 109 corresponds to the inlet portion and the shoulder portion of the PET bottle B having a height of about 22 cm accommodated in the outer electrode 106 in the outer electrode 106 (the position of 11 cm from the top). ) Was inserted.

<Coating condition>

Circumferential spacer 109: Hotbell (trade name, manufactured by Smithkin Ceramics Co., Ltd.).

Ground shield pipe 124: stainless steel.

Inner diameter of the gas flow path 127 of the inner electrode 126: 4 mm.

Medium: C ₂ H ₂ gas.

Gas flow rate of the medium: 40 to 80 sccm.

Gas pressure in PET bottle B and exhaust pipe 112: 0.08 to 0.2 Torr

High frequency power supplied to the internal electrode 126: 100 MHz, 250 W.

High frequency power applied to the external electrode 106: 13.56 MHz, output 250 W.

The thickness from the inlet part to the bottom part of the PET bottle which coated the carbon film by Example 8 and the above-mentioned conventional example 2 was measured. The result is shown in FIG.

13, in Example 8 in which the cylindrical spacer 109 made of a hot bell was inserted into the outer electrode 114 corresponding to the inlet and the shoulder of the PET bottle B, the entire surface of the PET bottle B was uniform. It can be clearly seen that the carbon film is coated.

On the other hand, in the conventional example 2 shown in FIG. 18 which stores the bottom part side in contact with the inner surface of the external electrode 201 from the inlet part of PET bottle B, from the inlet part among the inner surfaces of PET bottle B. In FIG. It can be seen that a thick carbon film is coated on the inner surface near the shoulder portion, resulting in uneven thickness of the carbon film. In addition, in Example 2, the thickness of the location which is 5 cm in height was not written because the thickness of the carbon film in the location had peeled thick.

(Example 9)

In the carbon film forming apparatus shown in FIG. 11 described above, the shoulder portion from the inlet portion of the PET bottle B is disposed within the cavity 108 of the spacer 109 made of a dielectric material, without the ground shield tube disposed on the outer circumference of the gas supply tube. The PET bottle B was subjected to the same conditions as in Example 8 except that the inner surface of the bottle B was brought into contact with or close to the inner surface thereof, and the bottom side was brought into contact with or near the inner surface of the external electrode 106 from the shoulder portion of the bottle B. ) Carbon coating on the inner surface.

In Example 8 and Example 9, when the high frequency electric power of 13.56 MHz and the output 250W was applied to the external electrode 106, and the gas pressure in PET bottle B and the exhaust pipe 112 was 0.2 Torr, the internal electrode 126 was carried out. The bias voltage for was measured. The results are shown in Table 1.

Table 1

Torr Bias voltage (V) Example 9 Example 8 0.2 -One -420

From Table 1, it can be clearly seen that in Example 8 according to the fourth embodiment, a bias voltage of about -420 V can be applied at a pressure of 0.2 Torr. On the other hand, in Example 9 having no ground shield tube, it can be seen that the bias voltage can hardly be applied toward the internal electrode 126 even when the same high frequency power is applied. This is because, in Example 8, the grounded ground shield pipe 124 can be used as the reference potential of the external electrode 106 by arranging the grounded ground shield pipe 124 on the outer periphery of the gas supply pipe 121.

According to this example 8, high-frequency power is supplied to the internal electrode 126 to generate a high-density plasma in the PET bottle B, and at the same time, the plasma is introduced into the external electrode 106 by the aforementioned bias voltage. It is possible to make a high-quality carbon film of uniform thickness on the inner surface of the PET bottle (B).

(5th embodiment)

14 is sectional drawing which shows the film forming apparatus on the inner surface of the plastic container which concerns on 5th Embodiment.

The carbon film forming apparatus of this fifth embodiment is the same as the carbon film forming apparatus of the fourth embodiment shown in FIG. 11 described above, except having the configuration described below. The ground shield tube 124 extends to the inner center vicinity of PET bottle B, and the surface area becomes large. The length of the internal electrode 126 was shortened by the length of the said ground shield pipe 124 long. The external electrode 106 extends to the vicinity of the inlet of the PET bottle B. As shown in FIG. The spacer 109 provided on the outer circumference of the PET bottle B inlet portion extends to the vicinity of the inlet of the PET bottle B like the external electrode 106.

In addition, as shown in FIGS. 14 and 15, the ground shield pipe 124 has a portion of its outer circumferential surface (the outer circumferential surface positioned in the exhaust pipe 112 and the outer circumferential surface immediately above the inner electrode 126) in order to increase the surface area. ] To the pin 132 is attached. In addition, the ground shield tube 124 has a bellows shape on a part of its outer circumferential surface (the outer circumferential surface portion located in the exhaust pipe 112 and the outer circumferential surface portion immediately above the inner electrode 126) in order to increase the surface area as shown in FIG. 16. The protrusions 133 may be formed.

In this fifth embodiment, the external electrode 106 is extended to the vicinity of the inlet of the PET bottle B, so that the bias power is applied to the external electrode 106 and the high-frequency power is supplied to the internal electrode 126. Plasma is generated inside the internal electrode 126 and the external electrode 106 (substantially inside the PET bottle B) and the exhaust pipe 112. At this time, the surface area of the ground electrode seen from this plasma is the sum of the surface areas of the fin 132 and the ground shield tube 124, and this surface area is increased in comparison with the above-described fourth embodiment. The sheath voltage generated between the plasma and the electrode is approximately inversely proportional to the area ratio of the electrode. Since the ratio of the surface area inside the PET bottle B located in the external electrode 106 and the surface area of the ground shield tube 124 becomes small, the sheath voltage generated between the external electrode 106 and the plasma, that is, the PET bottle B, The sheath voltage generated inside increases. The generation of a high sheath voltage inside the PET bottle B accelerates the ions in the PET bottle B and the incident energy to the inner surface of the PET bottle B becomes high. As a result, the carbon film having a good film quality can be coated by the inner surface of the PET bottle (B).

(6th Embodiment)

17 is an equivalent circuit diagram of a power supply system provided in the film forming apparatus on the inner surface of the plastic container according to the sixth embodiment.

The carbon film forming apparatus of the sixth embodiment has the same structure as the carbon film forming apparatus of the fourth embodiment shown in FIG. 11 described above except that the ground shield tube is not disposed on the outer circumference of the gas supply pipe.

As shown in FIG. 17, the bias power supply 114 is connected to the external electrode 106 via the cable 115. The matcher 117 is attached to the cable 115. The matcher 117 includes a first variable capacitor C1 mounted on the cable 115, and one end of the cable 115 between the bias power supply 114 and the first variable capacitor C1. The branch cable 161 branched from and grounded at the other end, and the second variable capacitor C2 attached to the branch cable 161 are constituted.

The high high frequency power supply 128 is connected to the internal electrode 126 via the cable 129. In addition, although the cable 129 is connected to the gas supply line (not shown), it demonstrates here by connecting to the internal electrode 126 conveniently. The matcher 131 is attached to the cable 129. The matcher 131 includes a first variable capacitor C1 ′ mounted to the cable 129, and a cable 129 between the high frequency power supply 128 and the first variable capacitor C1 at one end thereof. ) And a branched cable 162 branched from the other end and grounded, and a second variable capacitor C2 'attached to the branched cable 162. One end of the inductance L is connected to a conduction path between the matcher 131 and a gas supply pipe (not shown), and the other end is grounded.

According to this configuration, the bias power is applied from the bias power supply 114 to the external electrode 106 via the cable 115 and the bias matching device 117 as in the fourth embodiment described above. High high frequency power from the high high frequency power supply 128 is supplied to the internal electrode 126 through the cable 129 and the matching unit 131. As a result, discharge occurs between the internal electrode 126 and the external electrode 106 to generate a plasma. At this time, one end of the inductance L is connected to the conduction path between the matcher 131 and the gas supply pipe (not shown), and the other end is grounded to thereby connect the internal electrode 126 to which high high frequency power is applied. The external electrode 106 can function as a ground electrode. As a result, the bias voltage can be applied from the external electrode 106 toward the internal electrode 126, that is, toward the generated plasma, as in the fourth embodiment, without the ground shield pipe disposed on the outer periphery of the gas supply pipe.

As described above, according to the present invention, it is possible to provide a carbon film forming apparatus on the inner surface of a plastic container capable of coating a carbon film having a uniform film thickness on the entire inner surface of the plastic container.

According to the present invention, a carbon film having a uniform film thickness is coated on the inner surface, thereby providing a method for producing a plastic container having excellent barrier property against oxygen and carbon dioxide.

According to the present invention, a plastic container capable of introducing plasma generated in the plastic container by the bias voltage toward the inner surface of the container, and coating a carbon film having a good film quality and a uniform film thickness on the entire inner surface of the plastic container. A carbon film forming apparatus on the inner surface can be provided.

According to the present invention, a carbon film having a good film quality and having a uniform film thickness can be coated on the inner surface, thereby providing a method for producing a plastic container having better barrier to oxygen and carbon dioxide.

According to the present invention, high-frequency power is supplied to internal electrodes to generate high-density plasma in the plastic container, and the plasma can be drawn toward the inner surface of the container by a bias voltage. An apparatus for forming a carbon film on the inner surface of a plastic container capable of highway coating a carbon film having a film thickness over the entire inner surface of the plastic container can be provided.

According to the present invention, a carbon film having a good film quality and a uniform film thickness may be coated on the inner surface of a highway to provide a method for mass-producing a plastic container having better barrier against oxygen and carbon dioxide. .

The present invention provides a carbon film forming apparatus on an inner surface of a plastic container capable of coating a carbon film having a uniform film thickness on the entire inner surface of a plastic container, a method of manufacturing a plastic container coated on an inner surface of a carbon film having a uniform film thickness, and a film quality. A carbon film forming apparatus on the inner surface of a plastic container capable of coating a carbon film having a good and uniform film thickness on the inner surface of the plastic container, and a plastic film coated on the inner surface with a good film quality and a uniform film thickness. A method of producing a container, a carbon film forming apparatus on the inner surface of a plastic container capable of expressively coating a carbon film having a good film quality and having a uniform film thickness on the inner surface of the plastic container, and a good film quality and a uniform film thickness It is possible to provide a method for producing a plastic container having a carbon film having an inner surface coated with a highway. is.

Claims (13)

When connected to a high frequency power source and having a plastic container inserted therein, the external electrode has a size surrounding the container, the external electrode consisting of an external electrode body and an external electrode bottom member, an exhaust pipe communicating with the external electrode body, and inserted into the container. A device for forming a barrier film on an inner surface of a plastic container having a plurality of inner electrodes, wherein a plasma is generated between the outer electrode and the inner electrode to form a plasma in the presence of a medium gas supplied from the inner electrode. To The support member has a cylindrical upper and lower flanges, the upper flange is fixed to the exhaust pipe, and the lower flange is positioned on the base, The external electrode is disposed in a space surrounded by the base and the support member such that the external electrode main body is suspended and fixed to the exhaust pipe via an insulating member, and the external electrode bottom member is installed through the insulator on the base, The lower flange of the support member is opened and closed by integrally moving the base, the insulator and the external electrode bottom member with a pusher when the plastic container is detached from the bottom, and at the same time the bottom of the external electrode body disposed in the support member. Part is opened and closed Blocking film forming apparatus on inner surface of plastic container. The method of claim 1, The base and the support member positioned on the base via the lower flange are electrically connected to each other and grounded, and constitute an electronic shield member with respect to the external electrode disposed therein. Blocking film forming apparatus on inner surface of plastic container. The method of claim 1, The cylindrical support member is secured to the grounded exhaust pipe at its upper end. Blocking film forming apparatus on inner surface of plastic container. delete The method of claim 1, When the container is inserted, further comprising a spacer made of a dielectric material interposed between at least the inlet and shoulder portions of the container and the external electrode Blocking film forming apparatus on inner surface of plastic container. The method of claim 5, The spacer extends from the shoulder portion of the container and towards the bottom. Block-type device on the inner surface of a plastic container. The method of claim 1, The inner electrode is made of tungsten or stainless steel Blocking film forming apparatus on inner surface of plastic container. The method of claim 1, The high frequency power source is connected to a feed terminal provided on the external electrode. Blocking film forming apparatus on inner surface of plastic container. The method of claim 8, The high frequency power supply is connected to the external electrode, and a matching device for matching impedance is connected between the external electrode and the high frequency power supply, and a coaxial provided between the high frequency power supply and the matching device and between the matching device and the external electrode. The power supply terminals for cable connection are each connected by a coaxial cable. Blocking film forming apparatus on inner surface of plastic container. The method of claim 1, The film having excellent barrier properties is a carbon film Blocking film forming apparatus on the inner surface of the plastic container. The method of claim 1, The internal electrode has a cap having a gas injection hole formed at the tip thereof. Blocking film forming apparatus on inner surface of plastic container. When the cylindrical shape has a flange on the upper and lower ends, the upper flange is fixed to the exhaust pipe, and the lower flange is disposed in a space surrounded by the support member and the base and the support member, and the plastic container is inserted. The outer electrode body and the bottom of the outer electrode body, which have a size that surrounds the container and are suspended through the insulating member to the exhaust pipe and are fixed to the base, are disposed through the insulator with respect to the base, and are detachable together with the base and the insulator. The external electrode, which is composed of an external electrode bottom member, and the base, the insulator, and the external electrode bottom member are integrally moved up and down when the plastic container is detached and fixed in the lower flange of the support member and the support member. A pusher for opening and closing a bottom portion of the external electrode body, An internal electrode which is inserted in the aircraft and supplies medium gas into the container, exhaust means for exhausting the gas between the external electrode and the container and the gas in the container through the exhaust pipe, and a high frequency power source connected to the external electrode; In manufacturing an inner surface barrier coated plastic container using a barrier film forming apparatus to an inner surface of a plastic container, (a) integrally separating the base, the insulator and the external electrode bottom member by the pusher to simultaneously open the bottom flange of the support member and the bottom of the external electrode body fixed in the support member; (b) inserting a plastic container into the outer electrode body; (c) the lower flange of the support member by integrally attaching the external electrode bottom member, the insulator and the base to the lower flange of the support member and the external electrode body fixed in the support member by the pusher. And closing the bottom of the outer electrode body together and accommodating the container in an outer electrode composed of the outer electrode body and the outer electrode bottom member; (d) exhausting the gas inside and outside the container by the exhaust means; (e) supplying a medium gas from the internal electrode into the container; (f) supplying high frequency power from the high frequency power source to the external electrode while generating electromagnetic shielding by the base and the cylindrical support member, generating a plasma in the container to decompose the medium gas in the container and Coating the barrier film on the inner surface; (g) returning the inside of the vessel to atmospheric pressure after stopping the exhaust of the high frequency power, the medium gas and the gas, and (h) the base, the insulator and the external electrode bottom member are integrally separated by the pusher to simultaneously open the bottom flange of the support member and the bottom of the external electrode body, and open the container in the external electrode body. Including the process of taking out Method for producing inner barrier coated plastic container. The method of claim 12, Performing the barrier film coating operation of the next plastic container in the order of (b) to (h) above Method of manufacturing inner barrier coating plastic container.

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