WO2008041386A1

WO2008041386A1 - Production device of gas barrier plastic container and its production method

Info

Publication number: WO2008041386A1
Application number: PCT/JP2007/058458
Authority: WO
Inventors: Keishu Takemoto; Tsuyoshi Kage; Masahisa Oikawa; Shigekazu Tada; Takeharu Kawabe; Yuichi Sakamoto; Masaki Nakaya
Original assignee: Mitsubishi Shoji Plastics Corporation; Youtec Co., Ltd.; Kirin Beer Kabushiki Kaisha
Priority date: 2006-09-29
Filing date: 2007-04-18
Publication date: 2008-04-10
Also published as: JP5032080B2; JP2008088471A

Abstract

A production device of a gas barrier plastic container in which productivity of a gas barrier plastic container is enhanced by reducing the periodic foreign matter removing work in an exhaust chamber and the subsequent exhaust passage and the replacing work of an external electrode incident to changing the profile of the container. In the device for forming a thin film having gas barrier properties on the inner wall face of a plastic container by a plasma CVD method, a dielectric spacer is arranged in a gap space defined between the inner wall face of an external electrode and the outer wall face of the plastic container. Assuming the combined capacitance of the capacitance of the plastic container itself and the capacitance of its internal space is C1, and the combined capacitance of the outer space of the plastic container out of the internal space of a film deposition unit including the internal space of a vacuum chamber and the internal space of the exhaust chamber is C2, the following relation is satisfied; C1>C2, and low frequency power of 400kHz-4MHz is supplied to the external electrode.

Description

Specification

Gas barrier plastic container manufacturing apparatus and manufacturing method thereof

Technical field

TECHNICAL FIELD [0001] The present invention relates to a gas noble plastic container manufacturing apparatus for forming a thin film having gas barrier properties on the inner wall surface of a plastic container by plasma CVD (chemical vapor deposition). Moreover, it is related with the manufacturing method of the container. The present invention also relates to a plasma CVD film forming apparatus that can suppress the generation of plasma outside the reaction chamber. It also relates to the manufacturing method of the container.

[0002] The present invention also relates to a technique for suppressing plasma generation outside a reaction chamber when a gas noble film is formed on the inner wall surface of a plastic container by a plasma CVD method.

Background art

[0003] Plastic containers are difficult to use for oxygen-sensitive beverages such as beer and sparkling liquor because the odor sorbs quickly and gasno-rear is inferior to cans. Therefore, a method and apparatus for coating a hard carbon film (diamond-like carbon (DLC)) or the like that solves the problems of sorption and gas barrier properties in plastic containers are disclosed. For example, by using an external electrode having an internal space approximately similar to the outer shape of the target container and an internal electrode inserted into the container from the mouth of the container and also serving as a source gas introduction pipe, An apparatus for coating a hard carbon film on a wall surface is disclosed (for example, see Patent Document 1 or 2). In such an apparatus, high-frequency power is applied to the external electrode while a carbon source gas such as aliphatic hydrocarbons or aromatic hydrocarbons carbon is supplied as a source gas in the container. At this time, the source gas is turned into plasma between both electrodes, and ions in the generated plasma are attracted to a high-frequency potential difference (self-bias) generated between the external electrode and the internal electrode, and collide with the inner wall of the container. A film is formed.

[0004] Patent Document 1: Japanese Patent No. 2788412

Patent Document 2: Japanese Patent No. 3072269

Disclosure of the invention

Problems to be solved by the invention However, the present inventors have found that in such a film forming apparatus, the generation of plasma occurs not only in the external electrode in which the plastic container is accommodated, but also in the exhaust chamber communicating therewith. It has been found that some of the exhaust paths from the exhaust chamber to the vacuum pump occur.

[0006] Such plasma generated outside the external electrode may cause deterioration of metal parts in the exhaust chamber, metal parts such as pipes in the exhaust passage, and non-metal parts used in pipe joints, etc. Incurs shortening.

[0007] In addition, the plasma generated at other than the external electrode causes foreign material such as carbon-based foreign matter from the source gas to adhere to the wall surfaces of the exhaust chamber and the exhaust path. It is preferable that this carbon-based foreign matter is periodically removed.

[0008] Further, since the plasma generated outside the external electrode shifts the central portion of the plasma generated at the external electrode toward the exhaust chamber, a thick thin film is formed on the shoulder and mouth of the plastic container. This was the cause of non-uniform film thickness with respect to the main axis direction. Such a container having a non-uniform film thickness with respect to the container main axis direction may not be aesthetically pleasing.

[0009] Further, as long as an external electrode having an internal space that is almost similar to the outer shape of the target container is used as in the film forming apparatus disclosed in Patent Document 1 or 2, if the shape of the container differs, The external electrode corresponding to the above must be mounted on the film forming apparatus, which increases the cost of the apparatus. In addition, since it takes time to replace the external electrode, the operating rate of the film forming apparatus decreases.

[0010] Therefore, an object of the present invention is to prevent the generation of carbon-based foreign matter by suppressing the generation of plasma in the exhaust chamber or the exhaust path after that in the apparatus for manufacturing a gas plastic plastic container. In addition, it is not necessary to replace the external electrode when forming a film in containers having different shapes. The purpose is to increase the productivity of gas barrier plastic containers by reducing the work of removing external electrodes that accompanies periodic foreign object removal and container shape change. At the same time, it aims to prevent shortening of the device life.

[0011] Further, an object of the present invention is to produce a container having high uniformity of thin film thickness in the apparatus container main axis direction in the gas barrier plastic container manufacturing method. is there. [0012] Another object of the present invention is to provide a method for suppressing the generation of plasma in the exhaust chamber. Another object of the present invention is to provide a method for manufacturing a container in which the thickness of the gas barrier thin film is made uniform with respect to the container main axis direction by utilizing this plasma generation suppressing method. Furthermore, an object of the present invention is to provide an apparatus for producing a gas-nore plastic container that can operate stably for a long period of time, in which the deterioration of each component in the exhaust chamber and the exhaust path is difficult to occur by using this plasma generation suppression method. And

[0013] Further, if plasma leaks outside the reaction chamber, the impedance is not determined by the plastic container, the external electrode, and the internal electrode. Actually, the plastic container, the external electrode, the exhaust chamber, the exhaust pipe, and the internal electrode The impedance is considered to be determined between the two. Therefore, as the film is deposited, the carbon-based foreign material, which is an insulator, adheres to the film, and the impedance gradually increases. For example, in the film forming apparatus disclosed in Patent Document 1, Patent Document 2, and the like, the high frequency power source is not directly connected to the external electrode but connected via an automatic matching device. This is because the automatic matching device can match the impedance by the inductance recapacitance C so that the reflected wave from the entire electrode supplying the output is minimized. Since carbon-based foreign matter gradually accumulates on the wall, the change in impedance from one film formation to the next is very small. In such a case, the automatic matching unit is used in the same way as the fixed matching unit. On the other hand, long-term changes in impedance are handled by automatic matching. However, the carbon-based foreign matter may become thick and peel from the wall due to internal stress. When such delamination occurs, the impedance may change suddenly and plasma ignition may not occur. As a result, film formation may not occur at all, or even if ignition occurs, it may become very unstable. is there. If this happens, bottles with insufficient gas barrier properties will be unpredictably generated.

[0014] Therefore, an object of the present invention is to provide plasma in an exhaust chamber or an exhaust path thereafter so that plasma is generated only in the reaction chamber, that is, in the plastic container, in the plasma CVD film forming apparatus. This is to suppress the generation of plasma and to ignite the plasma stably at this time. Furthermore, by suppressing the generation of plasma in the exhaust chamber or in the exhaust path after that, it is possible to prevent the device life from being shortened, to prevent accidental occurrence of defective bottles due to a sudden change in impedance, and to the container main axis direction. Average thickness of gas barrier thin film The purpose is to unify. Another object of the present invention is to reduce the film thickness of the gas barrier thin film relative to the container main axis direction by suppressing the generation of plasma in the exhaust chamber or the exhaust path after it in the gas barrier plastic container manufacturing method. Is to produce a uniform container stably.

Means for solving the problem

The apparatus for producing a gas-no plastic plastic container according to the present invention includes an external electrode serving as a vacuum chamber that accommodates the plastic container, and a source gas supply pipe that is detachably disposed inside the plastic container. An internal electrode, a vacuum pump for exhausting the gas inside the external electrode, a power source connected to the external electrode, an exhaust space communicating with the internal space of the external electrode and above the opening of the plastic container A gas barrier plastic container having a chamber, an insulating member that electrically insulates the external electrode and the exhaust chamber, and forming a thin film having a gas releasability on the inner wall surface of the plastic container by a plasma CVD method In the manufacturing equipment of

A spacer made of a dielectric material is disposed in a gap space between the inner wall surface of the external electrode and the outer wall surface of the plastic container; and

The combined capacitance of the capacitance of the plastic container itself and the capacitance of its internal space is C, and the film forming unit including the internal space of the vacuum chamber and the internal space of the exhaust chamber.

1

C is the combined capacitance of the outer space of the plastic container in the inner space of the knit.

2 when c> c holds, and

1 2

The power supply supplies low frequency power having a frequency of 400 kHz to 4 MHz to the external electrode.

[0016] In the gas barrier plastic container manufacturing apparatus according to the present invention, the plastic container has a shape in which a mouth portion is reduced in diameter with respect to the body portion, and the external electrode is formed of the plastic container. It has a cylindrical internal space having an inner diameter slightly larger than the body diameter, and the spacer includes an outer wall surface of a portion whose diameter is reduced from the body portion to the mouth portion of the plastic container and the outer electrode. It is preferably disposed in a gap space sandwiched between cylindrical inner wall surfaces. Efficiently apply a bias voltage to plastic containers with substantially the same body diameter and different shoulder or neck shapes without replacing the external electrodes Can do.

In the apparatus for producing a gas plastic plastic container according to the present invention, the external electrode is a force having an internal space for accommodating the entire plastic container, or the whole excluding the mouth of the plastic container. The case where it has the internal space which accommodates is included. A thin film having a gas barrier property can be formed on the inner wall of the mouth of the plastic container, or it can be non-deposited.

[0018] A method for producing a gas-nore plastic container according to the present invention includes a step of housing a plastic container in an external electrode serving as a vacuum chamber,

A step of disposing an internal electrode serving as a source gas supply pipe inside the plastic container, and a spacer made of a dielectric in a gap space between the inner wall surface of the external electrode and the outer wall surface of the plastic container And a process of

A step of evacuating a gas inside the external electrode by operating a vacuum pump; a step of blowing a raw material gas into the plastic container under reduced pressure; a capacitance of the plastic container itself and a static of the internal space thereof; The combined capacitance with the capacitance is C, and the film formation unit including the internal space of the vacuum chamber and the internal space of the exhaust chamber.

1

When the combined capacitance of the outer space of the plastic container is C

2

And C> C, the external electrode has a frequency of 400 kHz to 4 MHz.

1 2

Supplying low-frequency power, converting the source gas into plasma, and forming a thin film having gas barrier properties on the inner wall surface of the plastic container;

It is characterized by having.

[0019] The method for producing a gas-soluble plastic container according to the present invention includes a case where a carbon film, a silicon-containing carbon film, or a SiO film is formed as the thin film having gas barrier properties.

[0020] In addition, the inventors of the present invention combined the insulator spacer and the internal space of the exhaust chamber as compared with the state where the manufacturing apparatus described in Patent Document 1 or 2 is in normal operation. The present inventors completed the present invention by discovering that a gas barrier thin film can be formed in a state in which plasma generation in the exhaust chamber is suppressed if film formation is performed with the capacitance impedance increased intentionally. I let you. That is, the method for suppressing plasma generation outside the reaction chamber according to the present invention is a reaction method. After the plastic container is accommodated in the chamber, the vacuum pump is operated to cause the gas inside the reaction chamber to pass through an exhaust chamber that is electrically insulated from the reaction chamber by an insulator spacer. When the raw material gas is blown out under a predetermined reduced pressure inside the plastic container, high-frequency power is supplied to the reaction chamber to turn the raw material gas into plasma, and the plastic container When the gas barrier thin film is formed on the inner wall surface, the impedance A of the synthetic capacitance C between the plastic container and the internal space of the reaction chamber, the insulator spacer 1, and the internal space of the exhaust chamber Composite capacitance of C impi

2 Of the dances B, the impedance B is relatively increased with the impedance A as a reference to suppress the generation of plasma in the exhaust chamber.

[0021] In the method for producing a gas-noreous plastic container according to the present invention, after the plastic container is accommodated in the reaction chamber, the vacuum pump is operated so that the internal gas in the reaction chamber is supplied by an insulator spacer. The reaction chamber is then evacuated through an exhaust chamber that is electrically insulated from the reaction chamber, and then the reaction chamber is blown out under a predetermined reduced pressure within the plastic container. In the method of producing a gas barrier plastic container by supplying a high frequency power to a plasma to form the raw material gas and forming a gas barrier thin film on the inner wall surface of the plastic container, the plastic container and the reaction chamber Combined capacitance with space C impedance A, insulator spacer and exhaust chamber

1

Impedance B of impedance B of combined capacitance C with subspace is

2

The gas barrier thin film is formed in a relatively high state with respect to the dance A.

[0022] In the method for producing a gas-soluble plastic container according to the present invention, C> C, and

1 2

It is preferable to increase the impedance B by supplying low frequency power superimposed on the high frequency power. As a result, a gas barrier thin film can be formed with an increased impedance B by an electrical action without adding physical operation of the apparatus members during film formation.

In the method for producing a gas barrier plastic container according to the present invention, it is preferable to increase the impedance B by increasing the volume of the exhaust chamber. Impedance B can be increased by increasing the volume of the exhaust chamber during film formation. [0024] In the method for producing a gas-soluble plastic container according to the present invention, it is preferable to increase the impedance B by changing the thickness of the insulator spacer to a thicker one. Impedance B can be increased by using a thick insulator spacer when forming the film.

In the method for manufacturing a gas barrier plastic container according to the present invention, a variable capacitor having a capacitance C is connected in series between the exhaust chamber and the ground, and the combined capacitance C

3 2 is the sum of the capacitance C of the variable capacitor.

Three

It is preferable to increase the impedance B by reducing the capacitance C. Deposit

Three

Impedance B can be increased by adjusting the capacitance of the variable capacitor.

In the method for producing a gas barrier plastic container according to the present invention, the frequency of the high frequency power is preferably 13.56 MHz.

[0027] In the method for manufacturing a gas barrier plastic container according to the present invention, the frequency of the low frequency power is preferably 100 kHz to 3 MHz. Impedance B can be sufficiently increased, and plasma generation in the exhaust chamber can be further suppressed.

[0028] In the method for producing a gas barrier plastic container according to the present invention, the output of the low frequency power is preferably 20 to 80% of the total output of the high frequency power and the low frequency power. While suppressing the generation of plasma in the exhaust chamber, the generation of plasma in the reaction chamber can be produced to produce a plastic container having good gas-releasability.

[0029] The method for producing a gas barrier plastic container according to the present invention includes a case where a carbon film, a silicon-containing carbon film, or a SiO film is formed as the gas barrier thin film.

[0030] The apparatus for producing a gas-no plastic plastic container according to the present invention electrically isolates each of the reaction chamber, the exhaust chamber, and the reaction chamber and the exhaust chamber, which accommodates the plastic container. And an insulator spacer provided with an opening for communicating the reaction chamber and the exhaust chamber, and an internal gas of the reaction chamber connected to the exhaust chamber via the opening and the exhaust chamber. A vacuum pump for exhausting gas, a source gas supply pipe disposed inside the plastic container, source gas supply means for supplying source gas to the source gas supply pipe, and high frequency power for supplying high frequency power to the reaction chamber And a gas barrier bra In the apparatus for manufacturing a stick container, the impedance A of the combined capacitance C between the plastic container and the internal space of the reaction chamber, the insulator spacer, and the exhaust chamber

1

Impedance B of impedance B of combined capacitance C with subspace is

2

It is characterized by the provision of an impedance increase means that is relatively high with respect to Dance A.

[0031] In the gas no plastic container manufacturing apparatus according to the present invention, C> C, and

1 2

The impedance increasing means is preferably low-frequency power supply means for supplying low-frequency power superimposed on high-frequency power supplied to the reaction chamber. As a result, the gas barrier thin film can be formed with the impedance B increased by an electrical action without applying physical manipulation of the apparatus members during film formation.

In the gas barrier plastic container manufacturing apparatus according to the present invention, the impedance increasing means is preferably means for increasing the volume of the exhaust chamber. By increasing the volume of the exhaust chamber at the time of film formation, it is possible to form a gas barrier thin film with increased impedance B.

[0033] In the gas-containing plastic container manufacturing apparatus according to the present invention, the impedance increasing means is preferably means for changing the insulator spacer to a thicker insulator spacer. It is possible to form a gas barrier thin film with an increased impedance B by making it possible to use a thick insulator spacer when forming the film.

[0034] In the apparatus for producing a gas plastic plastic container according to the present invention, it is preferable that the impedance increasing means is a variable capacitor connected in series between the exhaust chamber and the ground. By adjusting the capacitance of the variable capacitor when forming the film, it is possible to form a gas noor thin film with the impedance B increased.

[0035] Further, the inventors of the present invention have a device in which the combined capacitance of the inner space of the plastic container and the reaction chamber is larger than the combined capacitance of the inner space of the exhaust chamber and the insulator spacer, and By using a low-frequency power source as a power source to turn the raw material gas into plasma, the impedance on the exhaust chamber side is increased, thereby suppressing the occurrence of plasma in the exhaust chamber or the exhaust path thereafter. I found that I can do it. On the other hand, when using a low frequency power supply It was found that even if the plasma was not ignited or the plasma was ignited, the disappearance could occur accidentally, and as a measure against it, it was found that the incidental problem could be solved by providing auxiliary means for plasma ignition. Thus, the present invention has been completed. That is, the plasma CVD film forming apparatus according to the present invention includes a reaction chamber containing a plastic container, an exhaust chamber, and the reaction chamber and the exhaust chamber to electrically insulate each of the reaction chamber and the reaction chamber. And an insulator spacer having an opening communicating with the exhaust chamber, and connected to the exhaust chamber, and exhausts the internal gas of the reaction chamber through the opening and the exhaust chamber. A vacuum pump, a raw material gas supply pipe disposed inside the plastic container, a raw material gas supply means for supplying a raw material gas to the raw material gas supply pipe, and a low frequency power of a frequency of 100 kHz to 3 MHz in the reaction chamber. Low-frequency power supply means for supplying, and plasma ignition means having a spark generating portion disposed inside the plastic container, and the combined capacitance of the plastic container and the internal space of the reaction chamber is C age Said

1 If the combined capacitance of the insulator spacer and the internal space of the exhaust chamber is C, C>

It is characterized by the fact that 2 1 c is established.

2

[0036] In the plasma CVD film forming apparatus according to the present invention, it is preferable that the spark generating portion is disposed below the center of the height of the plastic container. A gas barrier thin film is easily formed on the bottom of the container and the film thickness distribution is easily homogenized.

[0037] In the plasma CVD film forming apparatus according to the present invention, the plasma ignition means includes a high-voltage DC power source, and the spark generation unit includes a spark electrode connected to the high-voltage DC power source, and a ground electrode. In addition, it is preferable to generate a spark between the spark electrode and the ground electrode. In this configuration, high-voltage DC power is used as an energy source for generating sparks.

[0038] In the plasma CVD film forming apparatus according to the present invention, the plasma ignition means has a distributor connected to the low-frequency power supply means, and the spark generator is a spark electrode connected to the distributor. And a ground electrode, and a spark may be generated between the spark electrode and the ground electrode. In this mode, low-frequency power is used as an energy source for generating sparks. Here, it is preferable that a phase shifter is connected in series between the distributor and the spark electrode. The occurrence of sparks In this mode, low-frequency power is used as a source of energy.

In the plasma CVD film forming apparatus according to the present invention, the spark electrode is formed of molybdenum, tantalum, zirconium, niobium, nickel, iridium, platinum, a base alloy of these metals, or carbon fiber. preferable. It is possible to suppress electrode consumption and contamination of the electrode material into the container. In addition, if the electrode material is carbon fiber, there is no risk of contamination of the electrode material when a carbon film is formed as a gas barrier thin film.

[0040] In the plasma CVD film forming apparatus according to the present invention, the source gas supply pipe is formed of a conductive material, and a linear or rod-like conductor is removed from the pipe except for its tip. And a gas flow path for blowing the source gas to the tip of the conductor, the conductor as the spark electrode, and the source gas supply pipe as the ground electrode It is preferred to be with. Even if the opening of the plastic container is small, the spark generation part can be placed on the main shaft inside the container, and it is difficult to cause uneven film thickness.

In the plasma CVD film forming apparatus according to the present invention, the source gas supply pipe is formed of a conductive material and is covered with an insulator except for its tip, and the source gas supply pipe , An outer tube made of a conductive material is disposed outside thereof, and has a double tube structure. The source gas supply tube is used as the spark electrode, and the outer tube is used as the ground electrode. It is also good to do. Even when the mouth of the plastic container is small, the spark generating part can be arranged on the main shaft inside the container, and it is difficult to cause non-uniform film thickness.

[0042] In the method for producing a gas-soluble plastic container according to the present invention, the step of accommodating the plastic container in the reaction chamber and the operation of the vacuum pump to bring the gas inside the reaction chamber into the insulator spacer Therefore, the step of exhausting through the exhaust chamber electrically insulated from the reaction chamber, the step of blowing the source gas into the plastic container under a predetermined reduced pressure, and the plastic container And C is the combined capacitance between the insulator spacer and the internal space of the exhaust chamber.

1 2 When the relationship C> C is established, the reaction chamber has a frequency of 100 kHz.

1 2

Supply low frequency power of ˜3 MHz and perform a forced spark inside the plastic container to make the source gas into plasma, and gas is applied to the inner wall of the plastic container. And a step of forming a barrier thin film. Containers with uniform gas barrier thin film thickness in the container main axis direction can be manufactured stably.

[0043] The method for producing a gas barrier plastic container according to the present invention includes forming a carbon film, a silicon-containing carbon film, or a SiO film as the gas barrier thin film.

The invention's effect

[0044] The present invention can suppress the generation of carbon-based foreign matter by suppressing the generation of plasma in the exhaust chamber or the exhaust path thereafter, in the gas barrier plastic container manufacturing apparatus. . In addition, when forming a film in a container having a different shape, it is not necessary to replace the external electrode. As a result, it is possible to reduce periodic foreign object removal work and external electrode replacement work associated with container shape change, and increase the productivity of gas barrier plastic containers. Furthermore, it is possible to prevent the apparatus life from being shortened.

[0045] Further, the present invention provides a method for producing a gas barrier plastic container, which can increase the productivity and produce a container having a highly uniform thin film thickness in the apparatus container main axis direction. .

[0046] According to the present invention, it is possible to deposit a gas barrier thin film in a state where generation of plasma in the exhaust chamber is suppressed. As a result, in the gas barrier plastic container manufacturing apparatus, it is possible to prevent the deterioration of each component in the exhaust chamber and the exhaust path, and to operate stably for a long time.

[0047] In the plasma CVD film forming apparatus according to the present invention, it is possible to suppress the generation of plasma in the exhaust chamber or the subsequent exhaust path so that the plasma is generated only inside the reaction chamber. It can be ignited stably. In addition, by suppressing the generation of plasma in the exhaust chamber or in the exhaust path after that, it is possible to prevent shortening of the device life, prevent accidental occurrence of defective bottles due to sudden changes in impedance, and to the container main axis direction. Thus, the film thickness of the gas barrier thin film can be made uniform.

Brief Description of Drawings

FIG. 1 is a schematic configuration diagram showing a first mode (A) of a gas barrier plastic container manufacturing apparatus according to the present embodiment.

[Fig. 2] Corresponding to the gas barrier plastic container manufacturing equipment of the first form (A) (B) (C) 2 The circuit diagram of a polar discharge type is shown.

FIG. 3 is a schematic configuration diagram showing a second form (A) of the gas barrier plastic container manufacturing apparatus according to the present embodiment.

FIG. 4 is a schematic configuration diagram showing an apparatus for producing a gas barrier plastic container according to a first embodiment (B).

FIG. 5 is a schematic configuration diagram showing an apparatus for producing a gas barrier plastic container according to a second embodiment (B).

FIG. 6 is a schematic configuration diagram showing an apparatus for producing a gas barrier plastic container according to a third embodiment (B).

FIG. 7 is a schematic configuration diagram showing a gas barrier plastic container manufacturing apparatus according to a fourth embodiment (B).

[FIG. 8] A circuit diagram of a bipolar discharge type corresponding to the gas barrier plastic container manufacturing apparatus of the fourth embodiment (B) is shown.

FIG. 9 is a diagram showing a comparison of appearance images of a bottle formed 100 times under the conditions of Test 1 and a bottle formed 100 times in Test 4, where (a) shows Test 4 (Example), (b) Is test 1 (comparative example).

FIG. 10 is a schematic configuration diagram showing a plasma CVD film forming apparatus of a first embodiment (C).

FIG. 11 is a diagram for explaining the details of FIG. 10, in which (a) is a cross-sectional view taken along line AA, and (b) is a partially enlarged schematic view of a spark generating portion.

FIG. 12 is a schematic configuration diagram showing a plasma CVD film forming apparatus of a second embodiment (C).

FIG. 13 is a diagram for explaining the details of FIG. 12, in which (a) is a cross-sectional view taken along the line BB, and (b) is a partially enlarged schematic view of a spark generating portion.

FIG. 14 is a schematic configuration diagram showing a plasma CVD film forming apparatus of a third embodiment (C).

FIG. 15 is a schematic configuration diagram showing a plasma CVD film forming apparatus of a fourth embodiment (C).

[FIG. 16] A diagram showing a comparison of appearance images of a bottle formed 100 times under the conditions of Test 1 and a bottle formed 100 times in Test 2, with (a) showing Test 1 (Example) and (b) Is test 2 (comparative example). Explanation of symbols

1 Lower external electrode

2 Upper external electrode External electrode (vacuum chamber)

Insulation material

Exhaust chamber

Lid

Deposition unit

Plastic container (PET bottle)

Internal electrode (Raw gas supply pipe)

a Gas outlet

0, 37, 38 O-ring

1, 14, 17, 21

2, 18, 22, Vacuum / Noreb

3 Mass flow controller

5 Source gas generation source

6 Raw material gas supply means

9 Leakage source

0 Pressure gauge

3 Vacuum pump

4 Exhaust duct

6 Automatic matcher (matching box, M. BOX)

7 Power supply

0 Internal space of external electrode (vacuum chamber)

1 Internal space of exhaust chamber

2, 32a, 32b opening

5 Low frequency power supply means

6, 36a, 36b Spacer

00A Gas formable plastic container manufacturing apparatus of the first form (A) 00A Gas formable plastic container manufacturing apparatus B of the second form (A) Reaction chamber B, 4Ba insulator spacer

B Vacuum chamber

5 Figureta unit

60 Automatic aligner

70 Low frequency power supply

8 Automatic matching device

9 High frequency power supply

0B Internal space of reaction chamber

50 Low frequency power supply means

60 High-frequency power supply means

0 Automatic matching device

1 High frequency power supply

2 Sub-room

3 Movable partition

4 opening

5 Means to increase the volume of the exhaust chamber

0 Insulator spacer changer

0 Variable capacitor

00B Gas barrier plastic container manufacturing apparatus of the first form (B) 00B Gas barrier plastic container manufacturing apparatus of the second form (B) 00B Gas barrier plastic container manufacturing apparatus of the third form (B) 00B Fourth form ( B) Gas-nolia plastic container manufacturing equipment C Reaction chamber

C Insulator spacer

C Vacuum chamber

50 distributor

60 Automatic aligner

70 Low frequency power supply 280 switches

290 High voltage DC power supply

Internal space of 30C reaction chamber

350 Low frequency power supply means

40 Spark generator

41 Conductor

42 Insulator (insulator)

43 Gas flow path

44 outer pipe

45 Phase shifter

100C Plasma CVD deposition system of the first form (C)

200C Plasma CVD film deposition system of the second form (C)

300C Plasma CVD film deposition system of 3rd form (C)

400C Plasma CVD deposition system of 4th form (C)

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention should not be construed as being limited to these descriptions.

[0051] (Embodiment A)

The present embodiment will be described with reference to FIGS. In addition, the same code | symbol was attached | subjected to the common site | part * component. First, a gas barrier plastic container manufacturing apparatus according to this embodiment will be described.

FIG. 1 is a schematic configuration diagram showing a first mode (A) of a gas barrier plastic container manufacturing apparatus according to the present embodiment. FIG. 1 is a longitudinal sectional view, and this manufacturing apparatus has a rotationally symmetric shape about the main axis of the plastic container 8. Here, the main axis of the container almost coincides with the main axis of the internal electrode. As shown in FIG. 1, the manufacturing apparatus 100A for the gas plastic plastic container of the first form (A) is inserted into the external electrode 3 serving as a vacuum chamber for housing the plastic container 8 and the inside of the plastic container 8. It is in contact with the internal electrode 9, which is a source gas supply pipe that is detachably disposed, the vacuum pump 23 that exhausts the gas inside the external electrode 3, and the external electrode 3. A connected power source 27, an exhaust chamber 5 communicating with the internal space 30 of the external electrode 3 and the opening of the plastic container 8, and an insulating member 4 for electrically insulating the external electrode 3 and the exhaust chamber 5; Is a gas barrier plastic container manufacturing device that forms a thin film with gas barrier properties on the inner wall surface of the plastic container 8 by plasma CVD, and is sandwiched between the inner wall surface of the external electrode 3 and the outer wall surface of the plastic container 8 Spacer 36 having dielectric force is disposed in the gap space, and the combined capacitance of the capacitance of the plastic container 8 itself and the capacitance of the internal space is C, and the interior of the vacuum chamber 3 Inside space 30 and exhaust chamber 5

1

When the combined capacitance of the outer space of the plastic container 8 in the inner space of the film forming unit 7 including the space 31 is C, the relationship C> C is established, and the power source 27 has a frequency of 400 k.

2 1 2

Supply low frequency power of Hz to 4 MHz to the external electrode 3.

[0053] Spacer 36 made of a dielectric is provided in a gap space between the inner wall surface of external electrode 3 and the outer wall surface of plastic container 8 in order to prevent abnormal discharge when low-frequency power is applied. Deployed. Preferably, a spacer having a shape that substantially fills the gap space is disposed. Spacer 36 made of a dielectric is preferably formed of an inorganic material such as glass or ceramics, or a heat resistant resin. Preferably, polytetrafluoroethylene, tetrafluoroethylene, bar fluoroalkyl vinyl ether copolymer, tetrafluoroethylene, hexafluoropropylene copolymer, polyphenylene oxide, polyimide, polyethersulfone.

, Polyetherimide, polyphenylene sulfide or polyetheretherketone. The spacer 36 made of a dielectric is preferably formed in a ring shape so as to surround the plastic container 8. This ring shape may be divided into several parts.

[0054] The external electrode 3 is formed in a hollow with a conductive material such as metal to form a vacuum chamber, and has an internal space 30 for accommodating a plastic container 8 to be coated, for example, a PET bottle which is a container made of polyethylene terephthalate resin. Have. The external electrode 3 consists of an upper external electrode 2 and a lower external electrode 1, and the upper part of the lower external electrode 1 is below the upper external electrode 2 with a ring.

It is configured to be detachably attached via 10. The plastic container 8 can be mounted by detaching the lower external electrode 1 from the upper external electrode 2. The external electrode 3 includes the 0_ring 37 disposed between the insulating member 4 and the external electrode 3 and the upper external electrode 2 The outer force is sealed by an O-ring 10 disposed between the outer electrode 1 and the lower outer electrode 1. In FIG. 1, the external electrode 3 is divided into two parts, ie, the upper external electrode 2 and the lower external electrode 1, but it is divided into three or more parts for the sake of manufacturing and sealed with a ring. It's okay.

[0055] The plastic container 8 generally has a shape in which the mouth portion has a reduced diameter with respect to the body portion, but the details are not necessarily unified, and may be appropriately changed depending on the design of the container. Therefore, the shoulder shape, neck shape, or mouth shape of the container differs depending on the contents. In the gas barrier plastic container manufacturing apparatus according to this embodiment, the internal space 30 formed in the external electrode 3 is a cylindrical space, for example, so that the plastic container 8 can be accommodated even if the shape and capacity are different. A cylindrical or square cylindrical space is preferable. If the internal space 30 is a cylindrical space, even if the container has a different shoulder shape, neck shape, or mouth shape, it can be used in common without replacing the external electrode. As a result, the replacement work time of the external electrode and the production cost of the external electrode can be reduced. Figure 1 shows the case of a cylindrical shape.

Furthermore, the external electrode 3 preferably has a cylindrical internal space 30 having an inner diameter slightly larger than the body diameter of the plastic container 8. There is no need to place a spacer 36 made of an insulator around the trunk of the plastic container 8, and self-bias is easily applied. At this time, the spacer 36a made of a dielectric material is sandwiched between the outer wall surface of the plastic container 8 whose diameter is reduced from the body portion to the mouth portion and the cylindrical inner wall surface of the external electrode 3 as shown in FIG. It is preferable that the gaps are arranged in the gap space. It is possible to effectively apply a bias voltage to plastic containers with substantially the same body diameter and different shoulder or neck shapes. In addition, as shown in FIG. 1, it is preferable to dispose a spacer 36b made of a dielectric material in a gap space between the outer wall surface of the bottom of the plastic container 8 and the cylindrical inner wall surface of the external electrode 3.

[0057] The spacer 36 made of a dielectric material preferably has a shape that is substantially in contact with the outer wall surface of the plastic container 8. If the container shape is different, the shape of the gap space is different. It is preferable to replace each of them correspondingly.

In the apparatus for manufacturing a gas barrier plastic container according to the present embodiment, as shown in FIG. 1, the exhaust communicating with the internal space 30 of the external electrode 3 and the opening of the plastic container 8 is provided. It is preferable that the chamber 5 is provided and the insulating member 4 for electrically insulating the external electrode 3 and the exhaust chamber 5 is disposed between the external electrode 3 and the exhaust chamber 5. By providing the exhaust chamber 5, the gas pressure change in the internal space 30 can be moderated when the internal space 30 of the external electrode 3 is exhausted. The exhaust chamber 5 adjusts the gas flow when the source gas blown from the internal electrode 9 flows through the plastic container 8 and is exhausted from the mouth. The insulating member 4 prevents low frequency power from being directly applied to the exhaust chamber 5. Here, to electrically insulate means to insulate DC, and in the case of low frequency power, it becomes capacitive coupling, and very low frequency power flows through the exhaust chamber 5.

The insulating member 4 is disposed between the external electrode 3 and the exhaust chamber 5, and an opening 32 a is formed at a position corresponding to the position above the mouth of the plastic container 8. The opening 32a allows the external electrode 3 and the exhaust chamber 5 to be in air communication. The insulating member 4 is preferably formed of an inorganic material such as glass or ceramics, or a heat resistant resin. The insulating member 4 is more preferably made of a dielectric material having a small dielectric loss. Preferably, polytetrafluoroethylene, tetrafluoroethylene / barfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, polyphenylene oxide, polyimide, polyether Sulphone, polyetherimide, polyphenylene sulfide, or polyester ether ketone.

The exhaust chamber 5 is formed hollow with a conductive material such as metal and has an internal space 31. The exhaust chamber 5 is disposed on the insulating member 4. At this time, the exhaust chamber 5 and the insulating member 4 are sealed by the O-ring 38. In order to make the internal space 31 and the internal space 30 communicate with each other in air, an opening 32b having substantially the same shape is provided in the lower part of the exhaust chamber 5 in correspondence with the opening 32a. The exhaust chamber 5 is connected to a vacuum pump 23 through an exhaust path including a pipe 21, a pressure gauge 20, a vacuum valve 22, and the like, and the internal space 31 is exhausted.

[0061] By disposing the exhaust chamber 5 on the insulating member 4, the lid 6 is formed, the external electrode 3 is sealed, and the film forming unit 7 that can be sealed is assembled. At this time, the film forming unit 7 has two chambers, an internal space 30 of the external electrode 3 and an internal space 31 of the exhaust chamber 5, which are connected through the openings 32a and 32b. [0062] The plastic container according to the present invention is, for example, a plastic bottle, cup or tray. Includes containers used with lids or stoppers or sealed, or open without using them. The size of the opening is determined according to the contents. The plastic container 8 has a predetermined thickness with moderate rigidity, and does not include soft packaging material formed from a sheet material without rigidity. The filling of the plastic container according to the present invention is, for example, a beverage such as beer, sparkling liquor, carbonated beverage, fruit juice beverage, or soft drink, a pharmaceutical product, an agrochemical product, or a dry food product that dislikes moisture absorption.

[0063] The resin used when molding the plastic container 8 is, for example, polyethylene terephthalate resin (PET), polyethylene terephthalate-based copolyester resin (cyclohexane dimethanol instead of ethylene glycol as the alcohol component of the polyester) Copolymers that use styrene are called PETG, manufactured by Eastman Chemical), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin (pp), cycloolefin copolymer resin (C0C, cyclic olefin) Copolymer), ionomer resin, poly-4-methylpentene-1 resin, polymethyl methacrylate resin, polystyrene resin, ethylene vinyl alcohol copolymer resin, acrylonitrile resin, polyvinyl chloride resin, polysalt vinylidene resin The Styrene resins - amide resin, polyamideimide resin, polyacetal resin, polycarbonate resin, polysulfone resin, 4 dollars modified styrene resin, acrylonitrile - styrene Ren resins or acrylonitrile - butadiene. Of these, PET is particularly preferred.

[0064] The internal electrode 9 also serves as a raw material gas supply pipe, and a gas flow path is provided therein, through which the raw material gas passes. The tip of the internal electrode 9 is provided with a gas outlet 9a, that is, an opening of a gas flow path. One end of the internal electrode 9 is fixed by a wall of the internal space 31 of the exhaust chamber 5, and the internal electrode 9 is disposed in the film forming unit 7. When the plastic container 8 is set in the external electrode 3, the internal electrode 9 is disposed in the external electrode 3 and disposed inside the plastic container 8 from the mouth. That is, the internal electrode 9 is inserted into the internal space 30 of the external electrode 3 through the internal space 31 and the openings 32a and 32b with the upper part of the inner wall of the exhaust chamber 5 as the base end. The tip of the internal electrode 9 is disposed inside the plastic container 8. The internal electrode 9 is preferably grounded. The source gas supply means 16 introduces the source gas supplied from the source gas generation source 15 into the plastic container 8. That is, one side of the pipe 11 is connected to the base end of the internal electrode 9, and the other side of the pipe 11 is connected to one side of the mass flow controller 13 via the vacuum valve 12. The other side of the mass flow controller 13 is connected to a source gas generation source 15 via a pipe 14. This source gas generation source 15 generates hydrocarbon gas type source gas such as acetylene.

The thin film having gas barrier properties in the present invention refers to a thin film that suppresses oxygen permeation, such as a carbon film including a DLC (diamond-like carbon) film, a Si-containing carbon film, or a SiO film. As the source gas generated from the source gas generation source 15, a volatile gas containing the constituent elements of the thin film is selected. As the raw material gas for forming the thin film having gas barrier properties, a publicly known volatile raw material gas is used.

[0067] As the source gas, for example, when a DLC film is formed, aliphatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons, etc. that are gaseous or liquid at room temperature are used. Is done. In particular, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexane and the like having 6 or more carbon atoms are desirable. When used in food containers, aliphatic hydrocarbons, especially ethylene hydrocarbons such as ethylene, propylene or butylene, or acetylene hydrocarbons such as acetylene, arylene or 1-butyne are used from the viewpoint of hygiene. Is preferred. These raw materials may be used alone, but they can also be used as a mixture of two or more. Further, these gases may be diluted with a rare gas such as argon or helium. In addition, Si-containing hydrocarbon-based gas is used when depositing a silicon-containing DLC film.

[0068] The DLC film referred to in the present invention is an i-carbon film or a hydrogenated amorphous carbon film (a-C:

H), which includes a hard carbon film. The DLC film is an amorphous carbon film with SP ³ bonds. A hydrocarbon-based gas such as acetylene gas is used as a source gas for forming this DLC film, and a Si-containing hydrocarbon-based gas is used as a source gas for forming a Si-containing DLC film. By forming such a DLC film on the inner wall surface of a plastic container, a container that can be used one-way and in a returnable manner as a container for beer, sparkling liquor, carbonated beverage, sparkling beverage or the like is obtained. [0069] Further, when forming a silicon-containing DLC film, a Si-containing hydrocarbon gas is used. Examples of silicified hydrocarbon gas or silicic acid gas include tetrasalt silicate, silane (SiH), hexene.

4 Samethyldisilane, butyltrimethylsilane, methylsilane, dimethylsilane, trimethylsilane, jetylsilane, propylsilane, phenylsilane, methyltriethoxysilane, vinylenotriethoxysilane, butyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane , Organic trisilane compounds such as phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, otamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane (HMDSO), etc. Organosiloxane compounds are used. In addition to these materials, aminosilane, silazane and the like are also used.

In the case of forming an SiO film (silicon oxide film), for example, a mixed gas of silane and oxygen or a mixed gas of HMDSO and oxygen is used as a source gas.

The vacuum pump 23 exhausts the gas inside the film forming unit 7. That is, one end of the pipe 21 is connected to the exhaust chamber 5, the other end of the pipe 21 is connected to the vacuum valve 22, and the vacuum valve 22 is connected to the vacuum pump 23 via the pipe. This vacuum pump 23 is further connected to an exhaust duct 24. A pressure gauge 20 is connected to the pipe 21 to detect the pressure in the exhaust path. By operating the vacuum pump 23, the gas in the plastic container 8 and the gas in the internal space 30 of the external electrode 3 move to the internal space 31 of the exhaust chamber 5 through the openings 32a and 32b, and the gas in the internal space 31 Is sent to the vacuum pump 23 through the exhaust path including the pipe 21.

The film forming unit 7 is connected to a leak pipe 17, and the pipe 17 communicates with a leak source 19 (open to the atmosphere) via a vacuum valve 18.

[0073] The low-frequency power supply means 35 supplies the low-frequency power to the external electrode 3 to turn the raw material gas inside the plastic container 8 into plasma. The low frequency power supply means 35 includes a power source 27 and an automatic matching unit 26 connected to the power source 27, and the power source 27 is connected to the external electrode 3 via the automatic matching unit 26. When the low frequency power generated by the power source 27 is applied to the external electrode 3 and a potential difference is generated between the internal electrode 9 and the external electrode 3, the raw material gas supplied into the plastic container 8 is turned into plasma. The frequency of the power source 27 is preferably 400 kHz to 4 MHz. As described above, the exhaust chamber 5 receives low-frequency power due to capacitive coupling. However, if the frequency force ΜΗζ of the power source 27 is exceeded, the low-frequency power applied to the exhaust chamber 5 increases, so that plasma is easily generated in the internal space 31 of the exhaust chamber 5, and the internal space of the external electrode 3 is increased. 30 alone makes it difficult to generate plasma. Accordingly, foreign substances derived from the raw material gas such as carbon-based foreign substances are deposited in the internal space 31 and need to be cleaned. On the other hand, if the frequency of the power supply 27 is less than 400 kHz, poor ignition is caused.

In the gas barrier plastic container manufacturing apparatus according to the present embodiment, the combined capacitance of the capacitance of the plastic container 8 itself and the capacitance of its internal space is C, and the inside of the vacuum chamber 3 C> C, where C is the combined capacitance of the outer space of the plastic container 8 out of the inner space of the deposition unit 7 including the space 30 and the inner space 31 of the exhaust chamber 5.

2 1 2 is preferably satisfied. When low frequency power of 400 kHz to 4 MHz is applied, the generation of plasma in the exhaust chamber 5 or the exhaust path after it can be further suppressed.

Next, the principle by which the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed when low frequency power having a frequency of 400 kHz to 4 MHz is supplied to the external electrode 3 will be described. FIG. 2 shows a bipolar discharge circuit corresponding to the gas barrier plastic container manufacturing apparatus of the first embodiment (A). The AC power supply in the circuit shown in Figure 2 corresponds to power supply 27. C is a plus

1 represents the combined capacitance of the capacitance of the tic container 8 itself and the capacitance of its internal space. C is measured by connecting an LCR meter to the plastic container 8 and the internal electrode 9.

1

You can. An LCR meter is a device that can measure inductance (L), capacitance (C), and resistance (R). C is the internal space 30 of the vacuum chamber 3 and

2

This represents the combined capacitance of the outer space of the plastic container 8 in the inner space of the film forming unit 7 including the inner space 31 of the exhaust chamber 5. For example, it is the combined capacitance of the capacitance of the gap space sandwiched between the inner wall surface of the vacuum chamber 3 and the outer wall surface of the plastic container 8 and the capacitance of the inner space 31 of the exhaust chamber 5. When the insulating member 4 is disposed, the capacitance of the internal space corresponding to the opening 32a is added to C. Spacer 36 is also in the clearance.

2

When arranged so as to occupy almost, the capacitance of the spacer becomes the capacitance of the gap space. C connects an LCR meter to the inner wall of the external electrode 3 and the inner wall of the exhaust chamber 5. Can be measured. Z is the impedance of the plasma generated in the plastic container 8.

pi

Z represents the plasm generated outside the plastic container 8, for example, in the exhaust chamber 5.

2

Represents the impedance of the machine. In the circuit of Figure 2, both sides of Z and Z

pi 2

Represents the sheath. Current flowing through the entire circuit is I, current flowing through C side is I, C side

If the current flowing through 1 1 2 is I, the relationship 1 = 1 + 1 holds. here,

2 1 2 c imp

1

Dance A is indicated by the number 1. The impedance B of C is given by Equation 2. This

2

Where f is a low frequency.

(Equation 1) Impedance A = 1 / (2 fC)

1

(Equation 2) Impedance Β = ΐΖ (2 π Κ)

2

[0076] In the gas barrier plastic container manufacturing apparatus 100A of Fig. 1, the relationship of C> C is established.

1 2

It is preferably designed to stand. The internal space 30 of the external electrode 3 is preferably large enough to accommodate the plastic container 8 completely, but if it is larger than that, the capacity can be changed freely. You can do it. Further, the capacity of the internal space 31 of the exhaust chamber 5 or the material and thickness of the insulating member 4 may be freely changed and designed. A capacity variable means for the internal space 31 or the internal space 30 may be provided. Provide a means for changing the material of the insulating member 4 and / or a means for changing the thickness. For example, when manufacturing the device so that the capacity of the internal space 30 of the external electrode 3 is large, the relationship of C> C should be established in advance.

1 2

The insulation member 4 is made thicker, or the insulation member 4 is made of a material having a small relative dielectric constant, or the device is produced so that the capacity of the internal space 31 of the exhaust chamber 5 is increased. deep. Consider the case where low frequency power of 400 kHz is output from the power supply 27. In the manufacturing apparatus 100A of FIG. 1, the relationship C> C, preferably the relationship C >> C holds.

1 2 1 2

By designing in this way, as shown in Equation 3, impedance B can be relatively increased with impedance A as a reference. At this time, the generation of plasma in the internal space 30 of the plastic container 8 is left as it is, and only the generation of plasma in the internal space 31 of the exhaust chamber 5 can be suppressed. And I shown in Fig. 2 can be increased.

(Equation 3) Impedance B

(f = 400kHz) Z impedance A = C / C

(f = 400kHz) 1 2

[0077] On the other hand, the result of Equation 4 is obtained from Equation 1 and Equation 2. According to Equation 4, the difference (impedance B—impedance A) is f force, and when C-C is positive, that is, the relationship of C> C

1 2 1 2 It turns out that it grows only when it holds. c If so, the difference

1>> c

2

Become stronger.

(Equation 4) Impedance B—Impedance Α = 1/2 π ί · {(C —C) / C C}

1 2 1 2

[0078] The gas barrier plastic container manufacturing apparatus 100A of FIG.

1 2

Is designed so that the relationship c>> c holds, and the plasma energy of the source gas

1 2

By supplying low frequency power with a frequency of 400 kHz to 4 MHz as a source, the impedance B increases relatively with respect to the impedance A, so that the plasma in the exhaust path leading to the exhaust chamber 5 and then to the vacuum pump 23 can be obtained. Occurrence can be suppressed. As a result, damage due to plasma attack in the exhaust chamber or exhaust path can be reduced, and the amount of source gas-based foreign matter, for example, carbon-based foreign matter, can be reduced.

[0079] As described above, the plasma generation region can be adjusted by appropriately designing and setting the impedance in the manufacturing apparatus. Further, a magnetic field can be used to adjust the fine generation region or the density distribution of the plasma. Although the technology for adjusting the plasma density distribution using a magnetic field is well known, in the apparatus shown in FIG. 1, the plastic container 8 is inserted from the spacer 36 and / or the external electrode 3 by installing a permanent magnet or an electromagnetic magnet. A magnetic field can be applied in the direction with respect to the internal space. Alternatively, in the apparatus shown in FIG. 1, the magnets may be arranged so that the N pole and the S pole are aligned in a direction parallel to the main axis direction of the plastic container. When a plurality of magnets are arranged, they are arranged on a circumference centered on the main axis of the plastic container 8, and preferably arranged at equal intervals. The permanent magnet is, for example, Ne-Fe-B image stone.

[0080] Here, in order to improve the stability of the plasma ignition of the source gas, it is preferable to provide a pointed portion (not shown) in the internal electrode 9. More preferably, the gas outlet 9a of the internal electrode 9 is provided with a pointed head. Moreover, you may provide a forced ignition means (not shown). In order to assist secondary electron emission, a secondary electron emission material may be formed by coating a part of the surface of the internal electrode 9 with a secondary electron emission material. Secondary electron emission materials such as BeO, MgO, CaO, SrO, BaO etc. 2A group alkaline earth metal oxides, TiO, ZrO etc.

twenty two

Group 4A metal oxides, Group 2B metal oxides such as ZnO, Group 3A metal oxides such as Y 2 O

twenty three

3B group metal oxides such as AlO and GaO, and 4B group metal acids such as SiO, PbO and PbO , 3B group nitrides such as A1N, 3B group nitrides such as GaN and SiN, fluorides such as barium oxynitride, LiF, MgF and CaF, carbides such as SiC, diamond, carbon nanotube, DLC Carbon materials such as these are used alone or in combination. These compounds may be used. In MgO series, MgO-AlO, MgO-TiO, MgO-ZrO, MgO-

2 3 2 2

V〇, Mg〇-Zn〇, MgO-SiO, MgO-SiO-TiO, MgO_Ru〇, MgO-MnOx

2 5 2 2 2

, MgO-Cr〇 etc. In the BaO system, for example, there is BaTiO. Secondary electron emission

2 3 3

A small amount of rare earth oxides such as NbO, LaO or SeO may be added to the layer material.

twenty two

Les. The secondary electron emission layer is formed by a film formation method such as MOCVD, sputtering, thermal spraying, or sol-gel method.

FIG. 3 is a schematic configuration diagram showing a second mode (A) of the gas barrier plastic container manufacturing apparatus according to the present embodiment. Equipment for manufacturing gas plastic plastic containers shown in Fig. 1 In 10 OA, external electrode 3 has an internal space 30 that accommodates the entire plastic container 8. Force manufacturing equipment for gas plastic plastic containers shown in Fig. 3 Like 200A, it has an internal space 30 that accommodates the entire plastic container 8 except the mouth. Gas barrier property The plastic container manufacturing apparatus 100A can uniformly form a thin film having gas barrier properties on the inner wall of the mouth of the plastic container 8. The 200 A gas barrier plastic container manufacturing apparatus does not form a thin film with a gas barrier property only on the inner wall of the mouth of the plastic container 8, and uniformly applies to the remaining inner wall surface except the inner wall of the mouth of the plastic container 8. A film can be formed.

Next, a method for manufacturing the gas barrier plastic container according to this embodiment will be described. Unless otherwise noted, the case where the DLC film is formed as a thin film having gas barrier properties using the gas barrier plastic container manufacturing apparatus 100A of FIG. 1 will be described.

[0083] A method for producing a gas-nore plastic container according to the present invention includes a step of housing a plastic container in an external electrode serving as a vacuum chamber, and an internal electrode serving as a raw material gas supply pipe disposed inside the plastic container. A step of disposing a spacer having a dielectric force in a gap space between the inner wall surface of the external electrode and the outer wall surface of the plastic container, and operating a vacuum pump to A step of exhausting the internal gas, a step of blowing the source gas into the plastic container under reduced pressure, and the plastic The combined capacitance of the capacitance of the vacuum vessel itself and the capacitance of its internal space is assumed to be ^, and among the internal spaces of the film forming unit including the internal space of the vacuum chamber and the internal space of the exhaust chamber, When the synthetic capacitance of the outer space of the plastic container is C,

2 c 1> c

2 Under the condition that the relationship is established, supply low frequency power with a frequency of 400 kHz to 4 MHz to the external electrode, convert the source gas into plasma, and form a thin film having gas barrier properties on the inner wall surface of the plastic container. And a process.

[0084] (Plastic container housing step, internal electrode placement step, and spacer placement step with a dielectric)

The film forming unit 7 is opened to the atmosphere by opening the vacuum valve 18, and the lower external electrode 1 of the external electrode 3 is removed from the upper external electrode 2. A spacer 36a made of a dielectric is put in advance from the lower side of the upper external electrode 2 and fixed. Next, the plastic container 8 is inserted into the space in the upper external electrode 2 from the lower side of the upper external electrode 2 and installed in the internal space 30 of the external electrode 3. At this time, the internal electrode 9 is inserted into the plastic container 8. A spacer 36b made of a dielectric is fixed to the lower external electrode 1. Next, the lower external electrode 1 is attached to the lower part of the upper external electrode 2, and the external electrode 3 is sealed with an O-ring 10. By the above operation, the plastic container 8 is accommodated in the internal space 30 of the external electrode 3, and the internal electrode 9 is disposed inside the plastic container 8, and the inner wall surface of the external electrode 3 and the plastic container 8 are disposed. A spacer 36 made of a dielectric material is disposed in a gap space between the outer wall surfaces of the substrate.

[0085] (Exhaust process of gas inside external electrode)

Next, the inside of the plastic container 8 is replaced with a raw material gas and adjusted to a predetermined film forming pressure. That is, as shown in FIG. 1, after the vacuum valve 18 is closed, the vacuum valve 22 is opened, the vacuum pump 23 is operated, and the gas inside the external electrode 3 is electrically connected to the external electrode 3 by the insulating member 4. Exhaust through the exhaust chamber 5 insulated by Thereby, the inside of the film forming unit 7 including the inside of the plastic container 8 is exhausted through the pipe 21, and the inside of the film forming unit 7 is evacuated. The pressure in the film forming unit 7 at this time is 2.6 to 66 Pa, for example.

[0086] (Process of blowing material gas)

Next, the vacuum valve 12 is opened, and carbonization of acetylene gas or the like at the source gas generation source 15 is performed. Hydrogen gas is generated, this hydrocarbon gas is introduced into the pipe 14, and the hydrocarbon gas whose flow rate is controlled by the mass flow controller 13 is supplied to the gas outlet through the pipe 11 and the ground potential internal electrode (raw gas supply pipe) 9. Blow out from 9a. As a result, hydrocarbon gas is introduced into the plastic container 8. The film forming unit 7 and the plastic container 8 are maintained at a pressure suitable for the film formation of the DLC film (for example, about 6.6 to 665 Pa) by the balance between the controlled gas flow rate and the exhaust capacity. Let

[0087] (Film-forming process of thin film having gas barrier property)

Next, low frequency power (for example, 1 MHz) with a frequency of 400 kHz to 4 MHz is supplied to the external electrode 3 while the raw material gas is blown into the plastic container 8 under a predetermined reduced pressure. The raw material gas in the plastic container 8 is turned into plasma using low frequency power as an energy source. As a result, a DLC film is formed on the inner wall surface of the plastic container 8. That is, by supplying low frequency power to the external electrode 3, a bias voltage is generated between the external electrode 3 and the internal electrode 9, and the raw material gas in the plastic container 8 is plasmatized to generate hydrocarbon-based plasma. The DLC film is formed on the inner wall surface of the plastic container 8. At this time, the automatic matching unit 26 matches the impedance by the inductance recapacitance C so that the reflected wave from the entire electrode supplying the output is minimized. In the gap space between the inner wall surface of the external electrode 3 and the outer wall surface of the plastic container 8, since the spacer 36 made of a dielectric is disposed, abnormal discharge does not occur.

[0088] In the gas barrier plastic container manufacturing apparatus 100A in FIG.

1 2 Preferably low frequency of 400 kHz to 4 MHz with C>> C relationship established

1 2

By supplying wave power, it is possible to suppress the generation of plasma in the exhaust path leading to the exhaust chamber 5 and then the vacuum pump 23 as described in FIG. 2 and Equations 1 to 4. . As a result, damage caused by the attack of the plasma in the exhaust chamber 5 and the exhaust path can be reduced, and the generation amount of the foreign material in the source gas system can be reduced. Here, as the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed, the consumption of energy is directed to the generation of plasma in the internal space 30 of the external electrode 3 and the plasma is When the generated central portion is a portion from the shoulder portion to the mouth portion of the plastic container 8, the center portion moves to the trunk portion that is the center of the plastic container 8. Therefore, the film thickness distribution along the main axis direction of the container is uniform. It becomes.

[0089] By uniforming the film thickness distribution, the thickness of the DLC film on the inner wall surface of the mouth of the plastic container 8 becomes thinner compared to the conventional case, so that the DLC film is formed on the inner wall surface of the mouth. The resulting coloration is reduced and the design is improved.

[0090] By changing the shape of the spacer 36 made of a dielectric, it is possible to form a film on another plastic container having a different shape without changing the external electrode 3.

Next, the output of the low frequency power from the power source 27 is stopped, the plasma is extinguished, and the film formation of the DLC film is completed. At about the same time, the vacuum valve 12 is closed and the supply of the raw material gas is stopped.

Next, the vacuum pump 23 exhausts the hydrocarbon gas remaining in the film forming unit 7 and the plastic container 8. Then, the vacuum valve 22 is closed and the exhaust is finished. The pressure in the film forming unit 7 at this time is 6.6 to 665 Pa. Thereafter, the vacuum valve 18 is opened. Thereby, the film forming unit 7 is opened to the atmosphere.

In any case, the film formation time is as short as several seconds. The DLC film is formed to a thickness of 0.003-5 μm.

[0094] (Embodiment B)

The present embodiment will be described with reference to FIGS. 2 and 4 to 9. In addition, the same code | symbol was attached | subjected to common site | part components. First, the manufacturing apparatus of the gas barrier plastic container according to this embodiment will be described.

FIG. 4 is a schematic configuration diagram showing a first mode (B) of the gas barrier plastic container manufacturing apparatus according to the present embodiment. As shown in the gas barrier plastic container manufacturing apparatus 100B according to the first embodiment (B), the gas plastic plastic container manufacturing apparatus according to the present embodiment includes a reaction chamber 3B containing the plastic container 8, an exhaust chamber 5, The insulating spacer 4B provided with an opening 32 that is sandwiched between the reaction chamber 3B and the exhaust chamber 5 to electrically insulate each of the reaction chamber 3B and the exhaust chamber 5, and the exhaust chamber 5 A vacuum pump 23 that is connected and exhausts the internal gas of the reaction chamber 3B through the opening 32 and the exhaust chamber 5, a source gas supply pipe 9 disposed inside the plastic container 8, and a source gas supply pipe 9 A plastic container 8 and a raw material gas supply means 16 for supplying the raw material gas to the reaction chamber 3B and a high-frequency power supply means 360 for supplying the high-frequency power to the reaction chamber 3B. reaction Chamber 3B inner space 30B combined capacitance C impedance A and insulator spacer 4

1

Impedance B of combined capacitance C of B and internal space 31 of exhaust chamber 5

2

Impedance increasing means is provided to increase dance B relative to impedance A as a reference.

[0096] (Manufacturing apparatus of first form (B))

In this embodiment, several forms are shown as the impedance increasing means. In the gas barrier plastic container manufacturing apparatus 100B according to the first embodiment (B), the impedance increasing means is a low-frequency power supply means 350 that superimposes low-frequency power on high-frequency power supplied to the reaction chamber 3B. is there.

[0097] In the present invention, there are a plurality of forms as a gas barrier plastic container manufacturing apparatus due to the difference in the configuration of the impedance increasing means. However, since the configuration other than the impedance increasing means has a common configuration, first, the common configuration is used. After the explanation, the impedance increasing means in the first embodiment will be explained.

[0098] The reaction chamber 3B is formed in a hollow shape with a conductive material such as metal, and has an internal space 30B for accommodating a plastic container 8 to be coated, for example, a PET bottle which is a container made of polyethylene terephthalate resin. The inner wall of the inner space 30B is formed in a shape that substantially contacts the outer shape of the plastic container 8. Since the reaction chamber 3B surrounds the plastic container 8, it acts as an external electrode. The reaction chamber 3B includes an upper external electrode 2 and a lower external electrode 1. The upper portion of the lower external electrode 1 is detachably attached to the lower portion of the upper external electrode 2 via a ring 10. . The plastic container 8 can be mounted by detaching the lower external electrode 1 from the upper external electrode 2. The reaction chamber 3B has an external force generated by the O-ring 37 disposed between the insulator spacer 4B and the reaction chamber 3B, and the 0_ring 10 disposed between the upper outer electrode 2 and the lower outer electrode 1. Sealed.

[0099] The insulator spacer 4B is disposed between the reaction chamber 3B and the exhaust chamber 5, and an opening 32a is formed at a position corresponding to the position above the mouth of the plastic container 8, The The opening 32a connects the reaction chamber 3B and the exhaust chamber 5 in air. The insulator spacer 4B is preferably formed of an inorganic material such as glass or ceramics or a heat resistant resin. Like Or polytetrafluoroethylene, tetrafluoroethylene “barfluoroalkyl bilayer copolymer”, tetrafluoroethylene “hexafluoropropylene copolymer”, polyphenylene oxide, polyimide, polyether. Sulphone, polyetherimide, polyphenylene sulfide or polyetheretherketone.

[0100] The exhaust chamber 5 is formed hollow with a conductive material such as metal and has an internal space 31. The exhaust chamber 5 is disposed on the insulator spacer 4B. At this time, the space between the exhaust chamber 5 and the insulator spacer 4B is sealed by the O-ring 38. In order to make the internal space 31 and the internal space 30B communicate with each other in air, an opening 32b having substantially the same shape is provided below the exhaust chamber 5 so as to correspond to the opening 32a. The exhaust chamber 5 is connected to a vacuum pump 23 through an exhaust path including a pipe 21, a pressure gauge 20, a vacuum valve 22, and the like, and the internal space 31 is exhausted.

[0101] By disposing the exhaust chamber 5 on the insulator spacer 4B, the lid 6 is formed, the reaction chamber 3B is sealed, and the sealable vacuum chamber 7B is assembled. At this time, the vacuum chamber 7B has two parts, an internal space 30B of the reaction chamber 3B and an internal space 31 of the exhaust chamber 5, which are connected through the openings 32a and 32b.

[0102] The source gas supply pipe 9 is made of a conductive material and also serves as an internal electrode.

The source gas supply pipe 9 has a tubular shape whose inside is hollow. A gas outlet 9a is provided at the tip. A gas outlet may be provided in the side cylinder of the source gas supply pipe 9. Further, the source gas supply pipe 9 (internal electrode) is grounded. One end of the raw material gas supply pipe 9 is fixed by a wall of the internal space of the exhaust chamber 5 and arranged in the vacuum chamber 7B. When the plastic container 8 is set in the reaction chamber 3B, the source gas supply pipe 9 is disposed in the reaction chamber 3B and disposed in the plastic container 8 from the mouth. That is, with the upper part of the inner wall of the exhaust chamber 5 as a base end, the source gas supply pipe 9 is inserted through the internal space 31 and the openings 32a and 32b to the internal space 30B of the reaction chamber 3B. The tip of the raw material gas supply pipe 9 is disposed inside the plastic container 8. The internal electrodes may be separately arranged without using the source gas supply pipe 9 and the internal electrodes. At this time, the internal electrode is grounded and inserted into the plastic container 8 in the same manner as the source gas supply pipe 9.

[0103] The container according to the present invention is the same as in the case of Embodiment A. [0104] The resin used in molding the plastic container 8 of the present invention is the same as that in the embodiment A.

The source gas supply means 16 introduces the source gas supplied from the source gas generation source 15 into the plastic container 8. That is, one side of the pipe 11 is connected to the base end of the source gas supply pipe 9, and the other side of the pipe 11 is connected to one side of the mass flow controller 13 via the vacuum valve 12. . The other side of the mass flow controller 13 is connected to a source gas generation source 15 via a pipe 14. This source gas generation source 15 generates hydrocarbon gas such as acetylene.

The gas barrier film in the present invention refers to a thin film that suppresses oxygen permeability, such as a DLC (diamond-like carbon) film, a Si-containing DLC film, a SiO film, an alumina film, or an A1N film. As the source gas generated from the source gas generating source 15, a volatile gas containing the constituent elements of the thin film is selected. As the raw material gas for forming the gas barrier thin film, a publicly known volatile raw material gas can be used.

[0107] As the source gas, for example, when forming a DLC film, it is the same as in the case of Embodiment A.

In the present invention, the DLC film is the same as in the case of Embodiment A.

[0109] Further, in the case of forming a silicon-containing DLC film, it is the same as in the case of Embodiment A.

[0110] When forming a SiO film (silicon oxide film), for example, a mixed gas of silane and oxygen or a mixed gas of HMDSO and oxygen is used as a source gas.

[0111] The vacuum pump 23 exhausts the internal gas of the vacuum chamber 7B. That is, one end of the pipe 21 is connected to the exhaust chamber 5, the other end of the pipe 21 is connected to the vacuum valve 22, and the vacuum valve 22 is connected to the vacuum pump 23 via the pipe. This vacuum pump 23 is further connected to an exhaust duct 24. A pressure gauge 20 is connected to the pipe 21 to detect the pressure in the exhaust path. By operating the vacuum pump 23, the internal gas of the plastic container 8 and the internal gas of the internal space 30B of the reaction chamber 3B move to the internal space 31 of the exhaust chamber 5 through the openings 32a and 32b, and the internal space 31 The internal gas is sent to the vacuum pump 23 through the exhaust path including the pipe 21.

[0112] The high frequency power supply means 360 supplies the high frequency to the reaction chamber 3B, The internal source gas is turned into plasma. The high-frequency power supply means 360 includes a high-frequency power supply 29 and an automatic matching device 28 connected to the high-frequency power supply 29, and the high-frequency power supply 29 is connected to the reaction chamber 3B via the automatic matching device 28. The high frequency power supply 29 generates high frequency power between the ground potential and the high frequency power is applied between the source gas supply pipe 9 (internal electrode) and the reaction chamber 3 B (external electrode). As a result, the raw material gas supplied to the inside of the plastic container 8 is turned into plasma. The frequency of the high-frequency power supply is more than 3MHz and less than 100MHz, and the high-frequency power supply 29 is preferably an industrial frequency of 13.56MHz, for example.

The vacuum chamber 7 B is connected to a leak pipe 17, and the pipe 17 communicates with a leak source 19 (open to the atmosphere) via a vacuum valve 18.

[0114] The gas barrier plastic container manufacturing apparatus according to the present embodiment has impedance increasing means based on the configuration described above. The impedance increasing means has a plurality of modes. In the gas barrier plastic container manufacturing apparatus 100B of the first mode (B), the low frequency power is supplied by superimposing the low frequency power on the high frequency power supplied to the reaction chamber 3B. The frequency power supply means 350.

[0115] The low-frequency power supply means 350 superimposes the low-frequency power on the high-frequency power and supplies it to the reaction chamber 3B, thereby converting the raw material gas inside the plastic container 8 into plasma. The low-frequency power supply means 350 includes a low-frequency power source 270 and an automatic matching unit 260 connected to the low-frequency power source 270. The low-frequency power source 270 is connected to the reaction chamber 3B via the automatic matching unit 260. The The low frequency power supply 270 generates low frequency power between the ground potential and the low frequency power between the source gas supply pipe 9 (internal electrode) and the reaction chamber 3B (external electrode). Applied by being superimposed on (by high frequency power supply 29). The frequency of the low-frequency power supply 270 indicates a relatively low frequency compared to the frequency of the high-frequency power supply 29, but if the frequency of the high-frequency power supply 29 is 13.56 MHz, the frequency of the low-frequency power supply 270 is 100 kHz to 3MHz is preferred. If the frequency of the low-frequency power supply 270 exceeds 3 MHz, the frequency difference from the frequency of the high-frequency power supply 29 (13.56 MHz) will be small, and the effect of increasing impedance B will be diminished. On the other hand, if the frequency of the low-frequency power supply 270 is less than 100 kHz, it may be difficult to discharge. [0116] In the manufacturing apparatus 100B of Fig. 4, in order to prevent the low-frequency power from being mixed into the high-frequency power source 29 and to prevent the high-frequency power from being mixed into the low-frequency power source 270, the automatic matching device 260, Connect a Fino Tunic 25 between 28 and reaction chamber 3B. Finale Tunic 25 includes HPF (High Pass Filter) and LPF (Low Pass Filter).

Next, the principle that the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed when the low frequency power is superimposed on the high frequency power will be described. Fig. 2 shows a bipolar discharge circuit corresponding to the gas barrier plastic container manufacturing apparatus of the first embodiment (B). The AC power supply of the circuit shown in Fig. 2 corresponds to the high frequency power supply 29 or the low frequency power supply 270. C represents the combined capacitance of the plastic container 8 and the internal space 30B of the reaction chamber 3B. C

1 can be measured by connecting an LCR meter to the plastic container 8 and the reaction chamber 3B. An LCR meter is an instrument that can measure inductance (L), capacitance (C), resistance (R), and so on. C is the inner space of insulator spacer 4B and exhaust chamber 5.

2

31 represents the combined capacitance. C is the LCR for insulator spacer 4B and exhaust chamber 5.

2

It can be measured by connecting a meter. Z is the plasma generated in the reaction chamber 3B.

pi

Z represents the impedance of the plasma generated in the reaction chamber 3B.

p2

is doing. In the circuit of Figure 2, each side of Z and Z represents a sheath.

pi 2

If the current flowing in the entire circuit is I, the current flowing in the C side is I, and the current flowing in the C side is I

1 1 2 2

, 1 = 1 +1 is established. Where the impedance A of C is given by

1 2 1

Is done. The impedance B of C is expressed by Equation 7. Where f is high frequency or low frequency

2

The frequency of the wave.

(Equation 6) Impedance A = 1 / (2 fC)

1

(Equation 7) Impedance Β = ΐΖ (2 π Κ)

2

[0118] The manufacturing apparatus 100B in Fig. 4 is designed so that the relationship of C> C is established.

1 2

Is preferred. If the inner space 30B of the reaction chamber 3B is substantially in contact with the outer surface of the plastic container 8, its size is limited by the shape of the plastic container 8, but the inner space 31 or insulator of the exhaust chamber 5 is limited. The material and thickness of the spacer 4B can be changed freely. Therefore, in order to establish the relationship C> C in advance, for example, insulator spacer 4

1 2

Increase the thickness of B, or use the insulator spacer 4B with a low relative dielectric constant. Therefore, a device is manufactured so that the capacity of the internal space 31 of the exhaust chamber 5 is increased. Consider a case where high frequency power of 13.56 MHz is output from the high frequency power supply 29 and low frequency power of 400 kHz is output from the low frequency power supply 270. The results of Equation 7 to Equation 8 are obtained.

(Equation 8) Impedance B Z Impedance B = 33.9

(f = 400kHz) (f = 13. 56MHz)

The result of Equation 8 is that if low frequency power (400 kHz) is supplied, impedance B is 33.9 times larger than when high frequency power (13.56 MHz) is supplied. As a result, a large voltage drop occurs in the internal space 31 of the exhaust chamber 5 and plasma generation occurs in the internal space 31 of the exhaust chamber 5.

[0119] In addition, the results of Equation 6 to Equation 9 are obtained.

(Equation 9) Impedance A / Impedance A = 33.9

(f = 400kHz) (f = 13. 56MHz)

[0120] The result of Equation 9 is that when low frequency power (400 kHz) is supplied, impedance A becomes relatively large compared to when high frequency power (13. 56 MHz) is supplied. This shows that a voltage drop occurs. However, in the manufacturing apparatus 100B shown in FIG. 4, it is possible to satisfy the relationship of C> C, preferably C >> C.

1 2 1 2

As shown in Fig. 3, impedance B can be relatively increased with reference to impedance A, and plasma generation in the internal space 31 of the exhaust chamber 5 is maintained while maintaining the generation of plasma in the internal space 30B of the reaction chamber 3B. Only can be suppressed. And I shown in Fig. 2 can be increased.

(Equation 10) Impedance B / Impedance A = C / C

(f = 400kHz) (f = 400kHz) 1 2

[0121] It should be noted that by designing such that the relationship C> C, preferably C>> C, is established.

1 2 1 2

As shown in Equation 11, impedance B can be relatively increased with reference to impedance A for plasma generation using high-frequency power as an energy source, and plasma is generated in internal space 30B of reaction chamber 3B. Can maintain the force to form a gas barrier thin film as it is, and tend to suppress only the generation of plasma in the internal space 31 of the exhaust chamber 5.

(Equation 11) Impedance B

(f = 13. 56MHz) Z impedance A = C / C

(f = 13. 56MHz) 1 2

[0122] On the other hand, impedance B is impeded by superimposing low-frequency power on high-frequency power. The increase relative to dance A is also indicated by finding the difference of impedance B minus impedance A. From Equation 6 and Equation 7, the result of Equation 12 is obtained. According to Equation 1 2, the difference (impedance B—impedance A) is f force M, then C — C

It can be seen that it increases only when 1 2 is positive, that is, when the relationship C> C holds. C

1 2 1

If the relationship >> c holds, the difference becomes larger.

2

(Equation 12) Impedance B—Impedance A = l / 2 f '{(C — C) / C C}

1 2 1 2

[0123] The manufacturing apparatus 100B of Fig. 4 is configured such that the relationship C> C, preferably the relationship C>> C holds.

1 2 1 2

By designing so that the low frequency power is superimposed on the high frequency power, the generation of plasma in the exhaust path to the exhaust chamber 5 and then to the vacuum pump 23 can be suppressed. As a result, the damage caused by the attack of the plasma in the exhaust chamber 5 and the exhaust path can be reduced, and the generation amount of the source gas dust can be reduced. At this time, the gas barrier thin film can be formed with the impedance B increased by an electrical action that does not control the physical operation of the apparatus members during film formation. Here, it is preferable to select a combination of power sources that increases the frequency difference between the high frequency and the low frequency.

[0124] (Manufacturing device of second form (B))

FIG. 5 is a schematic configuration diagram showing a second mode (B) of the gas barrier plastic container manufacturing apparatus according to the present embodiment. Differences from the manufacturing apparatus 100B of the first form (B) will be described. In the gas barrier plastic container manufacturing apparatus 200B of the second embodiment (B), a high frequency power source 51 is connected to a reaction chamber 3B (external electrode) via an automatic matching unit 50. However, a mechanism in which a low-frequency power source is connected and the low-frequency power is superimposed on the high-frequency power may be combined as in the manufacturing apparatus 100B of the first mode (B).

[0125] In the gas barrier plastic container manufacturing apparatus 200B of the second embodiment (B), the sub chamber 52 communicates with the exhaust chamber 5 through the opening 54 as an impedance increasing means. In the sub chamber 52, a movable partition 53 is provided. It is possible to adjust the volume V of the sub chamber 52 by moving the movable partition 53 closer to or away from the opening 54. In the gas noble plastic container manufacturing apparatus 200B of the second form (B), the impedance increasing means is means 55 for increasing the volume of the exhaust chamber 5, and comprises a sub chamber 52 and a movable partition 53. The present invention is not limited to the form in which the sub chamber 52 and the movable partition 53 are provided, and the volume of the exhaust chamber 5 is variable. Any structure can be used as long as it can. The volume of the internal space 31 of the exhaust chamber 5 (including V here) is 2.5 to 10 times the volume of the internal space 30B of the reaction chamber 3B.

1

Thus, it is preferable to design the volume of the sub chamber 52. If the volume of the exhaust chamber 5 is less than 2.5 times, the effect may be small, and if it exceeds 10 times, the sub chamber 52 will be too large.

Next, the principle that the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed when the volume of the exhaust chamber 5 is increased by the sub chamber 52 will be described. The bipolar discharge type circuit corresponding to the manufacturing apparatus 200 B in FIG. 5 is the same as the circuit shown in FIG. In this case, the AC power supply of the circuit shown in FIG. C with plastic container 8

1

It represents the combined capacitance with the internal space 30B of the reaction chamber 3B. C is an insulator spacer

2

1 represents the combined capacitance of 4B and the internal space 31 of the exhaust chamber 5. Here, the internal space 31 of the exhaust chamber 5 includes the internal space of the sub chamber 52 (a space equivalent to V). Ie V

1 1 The volume of the internal space 31 can be increased by increasing it. Z

The relationship of pi, Z, each P2 series, and 1 = 1 + 1 is the same as that of the manufacturing apparatus 100B in FIG. This

1 2

Here, the impedance A of C is expressed by Equation 6. The impedance B of C is the number 7

1 2

Indicated by. F is a high frequency and constant. Impedance A is therefore constant.

[0127] In general, the capacitance C of a capacitor is expressed by Equation 13. ε is the dielectric constant, S is the electrode area, and d is the distance between the electrodes.

(Equation 13) C = ε-S / d

[0128] When the movable partition 53 is powered to increase V, the approximate power of 13 is obtained.

1

D increases, and C decreases. Therefore, in number 7,

2

Peedance B increases. Here, since the impedance A is constant, the impedance B can be relatively increased with reference to the impedance A, and the gas barrier thin film is formed while maintaining the generation of plasma in the internal space 30B of the reaction chamber 3B. A film can be formed, and only the generation of plasma in the internal space 31 of the exhaust chamber 5 can be suppressed. As a result, the damage caused by the attack of the plasma in the exhaust chamber 5 and the exhaust path can be reduced, and the generation amount of the raw material gas dust can be reduced.

[0129] (Manufacturing apparatus of third embodiment (B)) FIG. 6 is a schematic configuration diagram showing a third mode (B) of the gas barrier plastic container manufacturing apparatus according to the present embodiment. Differences from the manufacturing apparatus 100B of the first form (B) will be described. In the gas barrier plastic container manufacturing apparatus 300B of the third embodiment (B), a high frequency power supply 51 is connected to a reaction chamber 3B (external electrode) via an automatic matching unit 50. However, a mechanism for connecting a low-frequency power source and superimposing the low-frequency power on the high-frequency power may be combined as in the manufacturing apparatus 100B of the first mode (B).

[0130] In the gas barrier plastic container manufacturing apparatus 300B of the third embodiment (B), the insulator spacer 4B (thickness t) is used as the impedance increasing means, and the thicker insulator spacer 4B a (thickness is used). Insulator spacer changing means 60 for changing to t) is provided. Insulation here

2

The thickness of the body spacer 4B corresponds to the average distance between the reaction chamber 3B and the exhaust chamber 5. The optimum thickness of the insulator spacer 4B varies depending on conditions such as the capacity of the container and the applied high frequency power and low frequency power, for example, 5 to 80 mm. In the third mode (B), not only when the insulator spacer 4B is completely replaced with the thicker insulator spacer 4Ba, but also the insulator spacer 4B is replaced with a separate insulator spacer. Including thicker insulator spacer 4Ba equivalent by stacking spacers. When changing the thickness of the insulator spacer 4B, the average distance between the reaction chamber 3B and the exhaust chamber 5 is also changed accordingly.

Next, the principle by which the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed when the insulator spacer 4B is changed to a thicker insulator spacer 4Ba will be described. The bipolar discharge circuit corresponding to the manufacturing apparatus 300B in FIG. 6 is the same as the circuit shown in FIG. In this case, the AC power supply of the circuit shown in FIG. C

1 represents the combined capacitance of the plastic container 8 and the internal space 30B of the reaction chamber 3B.

C represents the combined capacitance of the insulator spacer 4B and the internal space 31 of the exhaust chamber 5.

2

The For the relationship of Z, Z, each sheath and 1 = 1 + 1, the manufacturing apparatus 100B pi 2 1 2 in FIG.

Is the same as Here, the impedance A of C is expressed by Equation 6. C

1 2 Impedance B is given by Equation 7. F is a high frequency and is constant. Therefore, impedance A is constant.

[0132] If the insulator spacer 4B is changed to the thicker insulator spacer 4Ba, D leads to an increase and C decreases. Therefore, in equation 7,

2

One dance B increases. Here, since impedance A is constant, impedance B can be relatively increased with reference to impedance A, and a gas barrier thin film is formed while maintaining the generation of plasma in the internal space 30B of the reaction chamber 3B. In addition, only the generation of plasma in the internal space 31 of the exhaust chamber 5 can be suppressed. As a result, damage due to plasma attack in the exhaust chamber or exhaust path can be reduced, and the amount of dust in the source gas system can be reduced.

[0133] (Manufacturing device of the fourth form (B))

FIG. 7 is a schematic configuration diagram showing a fourth mode (B) of the gas barrier plastic container manufacturing apparatus according to the present embodiment. Differences from the manufacturing apparatus 100B of the first form (B) will be described. In the gas barrier plastic container manufacturing apparatus 400B of the fourth embodiment (B), a high frequency power source 51 is connected to a reaction chamber 3B (external electrode) via an automatic matching unit 50. However, a mechanism for connecting a low-frequency power source and superimposing the low-frequency power on the high-frequency power may be combined as in the manufacturing apparatus 100B of the first mode (B).

[0134] In the gas barrier plastic container manufacturing apparatus 400B of the fourth embodiment (B), a variable capacitor 70 connected in series is provided between the connection of the exhaust chamber 5 and the ground as an impedance increasing means. .

Next, the principle by which the generation of plasma in the inner space 31 of the exhaust chamber 5 is suppressed when the capacitance is changed by the variable capacitor 70 will be described. A bipolar discharge circuit corresponding to the manufacturing apparatus 400B of FIG. 7 is shown in FIG. FIG. 8 shows a bipolar discharge type circuit corresponding to the gas barrier plastic container manufacturing apparatus of the fourth embodiment (B). The AC power supply of the circuit shown in FIG. C with plastic container 8

1

It represents the combined capacitance with the internal space 30B of the reaction chamber 3B. C is a variable capacitor 7

Three

A capacitance of 0 is shown. C is the capacitance of insulator spacer 4B, C

2- 1 2- 2 indicates the capacitance of the exhaust chamber 5. C indicates the combined capacitance of C, C and C

2 2- 1 2- 2 3

is doing. Z and Z represent the impedance of each plasma, as in Figure 2. Figure

pi 2

In the circuit of 8, each side of Z and Z represents a sheath. To the whole circuit

pi P2

1 = 1 +1 where I is the current that flows, I is the current that flows to the C side, and I is the current that flows to the C side The relationship is established. Here, the impedance A of ^ is expressed by Equation 6. Here, f is a high frequency and is constant. Therefore, impedance A is constant.

[0136] Impedance B increases by reducing the capacitance C of variable capacitor 70.

Three

Here, since impedance A is constant, impedance B can be relatively increased with impedance A as a reference. Thereby, it is possible to form a gas barrier thin film while keeping the generation of plasma in the internal space 30B of the reaction chamber 3B as it is, and to suppress only the generation of plasma in the internal space 31 of the exhaust chamber 5. Can do. As a result, the damage caused by the attack of the plasma in the exhaust chamber 5 and the exhaust path can be reduced, and the generation amount of the raw material gas dust can be reduced.

[0137] Next, a method for manufacturing a gas barrier plastic container according to the present embodiment will be described. First, the manufacturing method according to the first embodiment (B) will be described with reference to FIG. In the manufacturing method according to the first mode (B), in order to increase the impedance B, C> C is set and a high-frequency

1 2

Superimpose low frequency power on the force. In general, make a device that satisfies the relationship c> c.

1 2

Make it. Hereinafter, a case where the DLC film is formed as a gas barrier thin film will be described as an example.

[0138] (Production method of the first form (B))

The inside of the vacuum chamber 7B is opened to the atmosphere by opening the vacuum valve 18, and the lower external electrode 1 of the reaction chamber 3B is removed from the upper external electrode 2. A plastic container 8 is inserted into the space in the upper external electrode 2 from the lower side of the upper external electrode 2 and installed in the internal space 30B of the reaction chamber 3B. At this time, the source gas supply pipe 9 is inserted into the plastic container 8. Next, the lower external electrode 1 is attached to the lower part of the upper external electrode 2, and the reaction chamber 3 B is sealed by the 0-ring 10.

[0139] Next, the inside of the plastic container 8 is replaced with a raw material gas and adjusted to a predetermined film forming pressure. That is, as shown in FIG. 4, after the vacuum valve 18 is closed, the vacuum valve 22 is opened, the vacuum pump 23 is operated, and the gas in the reaction chamber 3B is separated from the reaction chamber 3B by the insulator spacer 4B. Exhaust through the electrically insulated exhaust chamber 5. As a result, the inside of the vacuum chamber 7B including the inside of the plastic container 8 is exhausted through the pipe 21, and the inside of the vacuum chamber 7B becomes a vacuum. The pressure in the vacuum chamber 7B at this time is, for example, 2.6 to 66Pa. Next, the vacuum valve 12 is opened, a hydrocarbon gas such as acetylene gas is generated at the source gas generation source 15, this hydrocarbon gas is introduced into the pipe 14, and the hydrocarbon gas whose flow rate is controlled by the mass flow controller 13. Is blown out from the gas outlet 9a through the pipe 11 and the source gas supply pipe (internal electrode) 9 of the ground potential. As a result, hydrocarbon gas is introduced into the plastic container 8. The vacuum chamber 7B and the plastic container 8 are maintained at a pressure suitable for the formation of the DLC film (for example, about 6.6 to 665 Pa) by the balance between the controlled gas flow rate and the exhaust capacity. Let

[0140] Next, when high-frequency power (for example, 13.56 MHz) is supplied to the reaction chamber 3B when the raw material gas is blown out into the plastic container 8 under a predetermined reduced pressure, simultaneously or almost simultaneously. Suppose that low frequency power (eg 400 kHz) is superimposed on the high frequency power. At this time, the output of the low frequency power is preferably 20 to 80% of the total output of the high frequency power and the low frequency power. If the output of the low frequency power is less than 20%, the effect of suppressing the plasma generation in the exhaust chamber 5 is reduced, while if it exceeds 80%, the film formation rate may be slow. The supply timing of the high frequency power and the low frequency power may be shifted within the film formation time. At this time, since the filter unit 25 is connected, the high frequency power supply 29 is not affected by the low frequency, and the low frequency power supply 270 is not affected by the high frequency. Then, the raw material gas in the plastic container 8 is made into a plasma using high frequency power and low frequency power as energy sources. As a result, a DLC film is formed on the inner surface of the plastic container 8. That is, by supplying high frequency power and low frequency power to the reaction chamber 3B, a bias voltage is generated between the reaction chamber 3B and the source gas supply pipe 9 (internal electrode) 9, and the source gas in the plastic container 8 is plasma. Hydrocarbon plasma is generated and a DLC film is formed on the inner surface of the plastic container 8. At this time, the automatic matching devices 260 and 28 match the impedance by the inductance capacitance C so that the reflected wave from the entire electrode supplying the output is minimized.

[0141] In the manufacturing apparatus 100B of Fig. 4, the relationship of C> C, preferably the relationship of C>> C is established.

1 2 1 2

In the standing state, the low frequency power is superimposed on the high frequency power, so that the combined capacitance of the plastic container 8 and the internal space 30B of the reaction chamber 3B as explained in Fig. 2 and Equations 6 to 11 Impedance C of C, insulator spacer 4B, and the inner space 31 of the exhaust chamber 5 Of impedance B of capacitance C, impedance B is based on impedance A.

2

The gas barrier thin film is formed in a relatively high state. As a result, the generation of plasma in the exhaust chamber 5 and the subsequent exhaust path to the vacuum pump 23 is suppressed. As a result, the damage caused by the attack of the plasma in the exhaust chamber 5 and the exhaust path is small, and the generation amount of the raw material gas dust can be reduced.

[0142] Further, the following secondary effects can be obtained by superimposing low-frequency power on high-frequency power. When only low-frequency power is supplied, the deposition rate is reduced compared to when only high-frequency power is supplied. However, in the manufacturing method of the first mode (B), the deposition rate is equivalent when the low frequency of 400 kHz is superimposed and the total power is equal compared to the conventional discharge of 13.56 MHz alone. Or rise. In addition, the film thickness distribution along the main axis direction of the container is made uniform.

[0143] The boundary at which ions in the plasma can follow the high-frequency electric field can be evaluated by the ion plasma frequency. The ion plasma frequency is determined by the plasma density. As shown in Fig. 4, in the case of capacitively coupled plasma with bipolar discharge, the frequency is calculated to be approximately:! ~ 3 MHz. Therefore, with a high frequency discharge of 13.56 MHz, ions cannot follow the high frequency field. On the other hand, it can follow a 400kHz low frequency discharge. As in the device described in Patent Document 1, in 13.56MHz single discharge, ions are accelerated and incident on the bottle surface by self-bias. However, in the manufacturing method of the first form (B), ions can be accelerated by the high-frequency electric field (Vpp) with the superposition of 400 kHz. As a result, it is considered that ions having higher energy than before are incident on the inner surface of the plastic container 8. In addition, as the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed, energy is consumed for the generation of plasma in the internal space 30B of the reaction chamber 3B, and plasma is generated. When the central part is the part that reaches the shoulder mouth of the plastic container 8, it moves to the trunk that is the center of the plastic container 8. Therefore, the film thickness distribution along the main axis direction of the container is made uniform, and the film forming speed is improved or equivalent.

[0144] Since the film thickness distribution of the DLC film on the inner wall surface of the mouth of the plastic container 8 becomes thinner compared to the conventional case by making the film thickness distribution uniform, the DLC film is formed on the inner wall surface of the mouth. Origin of coloring Is reduced, and the design is improved.

Next, both the output of the high frequency power from the high frequency power supply 29 and the output of the low frequency power from the low frequency power supply 270 are stopped, the plasma is extinguished, and the film formation of the DLC film is completed. Almost at the same time, the vacuum valve 12 is closed to stop supplying the raw material gas.

[0146] Next, the vacuum pump 23 exhausts the hydrocarbon gas remaining in the vacuum chamber 7B and the plastic container 8. After that, the vacuum valve 22 is closed and the exhaust is finished. The pressure in the vacuum chamber 7B at this time is 6.6 to 665 Pa. After this, the vacuum valve 18 is opened. Thereby, the vacuum chamber 7B is opened to the atmosphere.

[0147] (Manufacturing method of the second form (B))

A manufacturing method according to the second embodiment (B) will be described with reference to FIG. In the manufacturing method according to the second mode (B), the volume of the exhaust chamber 5 is increased in order to increase the impedance B. Hereinafter, the difference from the manufacturing method according to the first embodiment (B) will be mainly described.

[0148] The process until the plastic container 8 is accommodated in the reaction chamber 3B and adjusted to a pressure suitable for the formation of the DLC film is the same as in the manufacturing method according to the first embodiment (B).

[0149] Next, when the source gas is blown into the plastic container 8 under a predetermined reduced pressure, the movable partition 53 of the sub chamber 52 is powered to increase the volume of V. Increase the volume of the exhaust chamber 5. Preferably, the position of the movable partition 53 is changed so that the volume of the exhaust chamber 5 is 2.5 to 10 times the volume. If the volume of the exhaust chamber 5 is less than 2.5 times, the effect may be small, and if it exceeds 10 times, the sub chamber 52 will be too large. Further, the volume including V in the internal space 31 of the exhaust chamber 5 with respect to the volume of the internal space 30B in the reaction chamber 3B is

1

It is preferable to increase the volume of the exhaust chamber 5 to be 5 times or more. Thereafter, high-frequency power (for example, 13.56 MHz) is supplied to the reaction chamber 3B. The timing for moving the movable partition 53 may be any time before supplying high-frequency power. Guidelines for increasing the volume of the exhaust chamber 5 are as follows. For example, when film formation is performed on a container having a small capacity of 0.3 L as the plastic container 8, the reaction chamber 3B in which the internal space 30B of the reaction chamber 3B is small can be formed of a small metal member. . As a result, C becomes smaller. You

1

In other words, impedance A increases. Therefore, increase V to increase the volume of exhaust chamber 5.

1

To reduce C and increase impedance B. As a result, the exhaust chamber 5 Generation of plasma can be suppressed. In the manufacturing method according to the second mode (B), the raw material gas in the plastic container 8 is turned into plasma using high frequency power as an energy source. As a result, a bias voltage is generated between the reaction chamber 3B and the raw material gas supply pipe 9 (internal electrode), and the raw material gas in the plastic container 8 is turned into plasma to generate hydrocarbon-based plasma. Is deposited on the inner surface of the plastic container 8. At this time, the automatic matching unit 50 matches the impedance by the inductance capacitance C so that the reflected wave from the entire electrode supplying the output is minimized. The film formation time at this time is as short as several seconds.

In the manufacturing apparatus 200B of FIG. 5, by increasing the volume of the exhaust chamber 5, the gas barrier thin film can be formed in a state where the impedance B is relatively increased with the impedance A as a reference. As a result, the generation of plasma in the exhaust path leading to the exhaust chamber 5 and then to the vacuum pump 23 is suppressed. As a result, the damage due to the plasma attack in the exhaust chamber 5 and the exhaust path is reduced, and the generation amount of the raw material gas dust can be reduced. In addition, as the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed, energy consumption is diverted to the generation of plasma in the internal space 30B of the reaction chamber 3B. When the center where the plasma is generated is the part from the shoulder to the mouth of the plastic container 8, it moves to the trunk which is the center of the plastic container 8. Therefore, the film thickness distribution along the main axis direction of the container is made uniform. By making the film thickness distribution uniform, the color derived from the DLC film on the inner wall surface of the mouth is reduced, and the design is improved.

Next, the output of the high frequency power from the high frequency power supply 51 is stopped. The subsequent steps up to the removal of the container are the same as in the manufacturing method of the first form (B).

[0152] (Manufacturing method of the third form (B))

A manufacturing method according to the third embodiment (B) will be described with reference to FIG. In the manufacturing method according to the third mode (B), in order to increase the impedance B, the insulator spacer 4B is changed to a thicker insulator spacer 4Ba. Hereinafter, the difference from the manufacturing method according to the first embodiment (B) will be mainly described.

[0153] The process until the plastic container 8 is accommodated in the reaction chamber 3B and adjusted to a pressure suitable for the formation of the DLC film is the same as that in the manufacturing method according to the first embodiment (B). [0154] Next, when the source gas is blown into the plastic container 8 under a predetermined reduced pressure, the insulator spacer 4B is changed to a thicker insulator spacer 4Ba. Preferably, the insulator spacer is changed to 4Ba having a thickness of 3 to 6 times. If the thickness is changed to less than 3 times, the effect may be small. If the thickness is changed to more than 6 times, the device will expand in the longitudinal direction and become larger. Thereafter, high-frequency power (for example, 13.56 MHz) is supplied to the reaction chamber 3B. Insulator spacers 4Ba can be changed anytime before high-frequency power is supplied. Here, the guidelines for thickening the insulator spacer 4B are as follows. For example, when a film is formed in a small container having a capacity of 0.3 liter as the plastic container 8, the reaction chamber 3B in which the internal space 30B of the reaction chamber 3B is small can be formed of a small metal member. . As a result, C becomes smaller. Snow

1

That is, impedance A increases. Therefore, by increasing the thickness of insulator spacer 4B, C

Decrease 2 and increase impedance B. Thereby, generation of plasma in the exhaust chamber 5 can be suppressed. Also in the manufacturing method according to the third mode (B), a DLC film is formed on the inner surface of the plastic container 8 using high-frequency power as an energy source, as in the manufacturing method according to the second mode (B).

[0155] In the manufacturing apparatus 300B of Fig. 6, by changing to the thicker insulator spacer 4Ba, the gas barrier thin film is formed in a state where the impedance B is relatively increased with the impedance A as a reference. . As a result, similarly to the manufacturing method according to the second mode (B), the damage due to the attack of the plasma in the exhaust chamber 5 and the exhaust path is suppressed, the amount of dust generated in the source gas system is reduced, and the main axis direction of the container is aligned. Uniform film thickness distribution and reduction of coloring derived from the DL C film on the inner wall of the mouth can be realized.

[0157] (Manufacturing method of the fourth form (B))

A manufacturing method according to the fourth embodiment (B) will be described with reference to FIG. In the manufacturing method according to the fourth mode (B), in order to increase the impedance B, a variable capacitor 70 having a capacitance C is connected in series between the connection between the exhaust chamber 5 and the ground, and the combined capacitance C ( However, variable

3 2

Impedance B is increased by reducing the capacitance (capacitance C of the capacitor). The Hereinafter, the difference from the manufacturing method according to the first embodiment (B) will be mainly described.

[0158] The process until the plastic container 8 is accommodated in the reaction chamber 3B and adjusted to a pressure suitable for forming the DLC film is the same as in the manufacturing method according to the first embodiment (B).

[0159] Next, the source gas is blown out into the plastic container 8 under a predetermined reduced pressure.

Thereafter, high frequency power (for example, 13.56 MHz) is supplied to the reaction chamber 3B. At this time, the capacitance C of the variable capacitor 70 is adjusted to be small. Variable capacitor 70

Three

The guidelines for adjusting the amount are as follows. For example, when film formation is performed in a small container having a capacity of 0.3 liter as the plastic container 8, the internal space 30B of the reaction chamber 3B is small. The reaction chamber 3B can be formed of a small metal member. As a result, C becomes smaller

1

. That is, the impedance A increases. Therefore, the capacitance C of the variable capacitor 70

Adjust C to decrease 3 to decrease C and increase impedance B. this

2

Thus, the generation of plasma in the exhaust chamber 5 can be suppressed. The optimum capacity of the variable capacitor 70 is a force that varies depending on the capacity of the target plastic container 8, for example, 5 to: 100 pF, preferably 10 to 80 pF. The timing of adjusting the capacity of the variable capacitor 70 can be any time before or during the supply of high-frequency power. In the manufacturing method according to the fourth mode (B), a DLC film is formed on the inner surface of the plastic container 8 using high-frequency power as an energy source, as in the manufacturing method according to the second mode (B). .

[0160] In the manufacturing apparatus 400B of Fig. 7, in order to increase the impedance B, the impedance B can be reduced by adjusting the capacitance C of the variable capacitor 70 to be small.

Three

The gas barrier thin film is formed in a relatively high state with respect to the flow rate A. As a result, as in the manufacturing method according to the second mode (B), the damage due to the plasma attack in the exhaust chamber 5 and the exhaust path is suppressed, the amount of dust generated in the source gas system is reduced, the main shaft of the container Uniform film thickness distribution along the direction and reduction of coloring derived from the DLC film on the inner wall of the mouth.

[0162] In each of the manufacturing methods according to the first to fourth embodiments (B), the film formation time is as short as several seconds. The DLC film is formed to a thickness of 0.003 to 5 xm. [0163] (Embodiment C)

The present embodiment will be described with reference to FIGS. 2 and 10 to 16. In addition, the same code | symbol was attached | subjected to common site | part parts. First, the plasma CVD film forming apparatus according to this embodiment will be described.

FIG. 10 is a schematic configuration diagram showing a first mode (C) of the plasma CVD film forming apparatus according to the present embodiment. FIGS. 11A and 11B are diagrams for explaining the details of FIG. 10, where FIG. 11A is a cross-sectional view taken along the line AA, and FIG. As shown in the plasma CVD film forming apparatus 100C of the first embodiment (C), the plasma CVD film forming apparatus according to this embodiment includes a reaction chamber 3C that accommodates a plastic container 8, an exhaust chamber 5, and a reaction chamber 3C. An insulating spacer 4C provided with an opening 32 for electrically insulating each of the reaction chamber 3C and the exhaust chamber 5 between the exhaust chamber 5 and the exhaust chamber 5 connected to the exhaust chamber 5. The vacuum pump 23 that exhausts the gas inside the reaction chamber 3C via the 32 and the exhaust chamber 5, the source gas supply pipe 9 arranged inside the plastic container 8, and the low frequency of 100 kHz to 3 MHz in the reaction chamber 3C A low-frequency power supply means 350 for supplying electric power and a plasma ignition means having a spark generating part 40 disposed inside the plastic container 8, and a combination of the plastic container 8 and the internal space 30C of the reaction chamber 3C. Capacitance C, insulator spacer 4C and exhaust chamber 5, inside

1

When the combined capacitance with space 31 is C, the relationship C> C is established.

2 1 2

[0165] In the present embodiment, several forms are shown as the plasma ignition means having the spark generator 40. In the plasma CVD film forming apparatus 100C, which is the first form (C), the plasma ignition means having the spark generating unit 40 is a DC discharge system using a high-voltage DC power supply 290.

[0166] In the present invention, there are a plurality of forms as a plasma CVD film forming apparatus due to the difference in the plasma ignition means having the spark generation part 40, but the configuration other than the plasma ignition means having the spark generation part 40 is common. First, after explaining the common configuration, the impedance increasing means in the first mode (C) will be explained.

[0167] The reaction chamber 3C is formed hollow with a conductive material such as metal, and has an internal space 30C for accommodating a plastic container 8 to be coated, for example, a PET bottle which is a container made of polyethylene terephthalate resin. The inner wall of the internal space 30C is outside the plastic container 8. It is formed in a shape that substantially contacts the wall surface. Since the reaction chamber 3C surrounds the plastic container 8, it acts as an external electrode. The reaction chamber 3C includes an upper external electrode 2 and a lower external electrode 1, and is configured such that the upper portion of the lower external electrode 1 is detachably attached to the lower portion of the upper external electrode 2 via a ring 10. . The plastic container 8 can be mounted by detaching the lower external electrode 1 from the upper external electrode 2. Reaction chamber 3C is sealed with external force by 0 ring 37 placed between insulator spacer 4C and reaction chamber 3C, and 0_ring 10 placed between upper outer electrode 2 and lower outer electrode 1. It has been.

[0168] The insulator spacer 4C is disposed between the reaction chamber 3C and the exhaust chamber 5, and an opening 32a is formed at a position corresponding to the position above the mouth of the plastic container 8, The The opening 32a connects the reaction chamber 3C and the exhaust chamber 5 in air. The insulator spacer 4C is preferably formed of an inorganic material such as glass or ceramics or a heat resistant resin. Preferably, polytetrafluoroethylene, tetrafluoroethylene “verfluoroalkylbierethenole copolymer”, tetrafluoroethylene “hexafluoropropylene copolymer”, polyphenylene oxide, polyimide, Polyethersulfone, polyetherimide, polyphenylene sulfide or polyetheretherketone.

The exhaust chamber 5 is formed hollow with a conductive material such as metal, and has an internal space 31. The exhaust chamber 5 is disposed on the insulator spacer 4C. At this time, the space between the exhaust chamber 5 and the insulator spacer 4C is sealed by the O-ring 38. In order to make the internal space 31 and the internal space 30C communicate with each other in air, an opening 32b having substantially the same shape is provided in the lower portion of the exhaust chamber 5 in correspondence with the opening 32a. The exhaust chamber 5 is connected to a vacuum pump 23 through an exhaust path including a pipe 21, a pressure gauge 20, a vacuum valve 22, and the like, and the internal space 31 is exhausted.

[0170] By disposing the exhaust chamber 5 on the insulator spacer 4C, the lid 6 is formed, the reaction chamber 3C is sealed, and the sealable vacuum chamber 7C is assembled. At this time, the vacuum chamber 7C has two parts, an internal space 30C of the reaction chamber 3C and an internal space 31 of the exhaust chamber 5, which are connected through the openings 32a and 32b.

[0171] The container according to the present invention is the same as in the case of Embodiment A. [0172] The resin used in molding the plastic container 8 of the present invention is the same as that in the embodiment A.

[0173] The raw material gas supply pipe 9 is provided with a gas flow path therein, through which the raw material gas passes. A gas outlet 9a, that is, an opening of a gas flow path is provided at the tip of the source gas supply pipe 9. One end of the source gas supply pipe 9 is fixed by the wall of the internal space 31 of the exhaust chamber 5 and is disposed in the vacuum chamber 7C. When the plastic container 8 is set in the reaction chamber 3C, the source gas supply pipe 9 is disposed in the reaction chamber 3C and disposed in the plastic container 8 from the mouth. That is, the raw material gas supply pipe 9 is inserted from the upper part of the inner wall of the exhaust chamber 5 to the inner space 30C of the reaction chamber 3C through the inner space 31 and the openings 32a and 32b. The tip of the source gas supply pipe 9 is disposed inside the plastic container 8. The raw material gas supply pipe 9 holds the force to be an electrode itself or an electrode of another part, which will be described later.

The raw material gas supply means 16 introduces the raw material gas supplied from the raw material gas generation source 15 into the plastic container 8. That is, one side of the pipe 11 is connected to the base end of the source gas supply pipe 9, and the other side of the pipe 11 is connected to one side of the mass flow controller 13 via the vacuum valve 12. . The other side of the mass flow controller 13 is connected to a source gas generation source 15 via a pipe 14. This source gas generation source 15 generates hydrocarbon gas source gas such as acetylene.

In the present invention, the gas barrier film refers to a thin film that suppresses oxygen permeability, such as a DLC (diamond-like carbon) film, a Si-containing DLC film, a SiO film, an alumina film, or an A1N film. As the source gas generated from the source gas generating source 15, a volatile gas containing the constituent elements of the thin film is selected. As the raw material gas for forming the gas barrier thin film, a publicly known volatile raw material gas can be used.

[0176] As the source gas, for example, when forming a DLC film, it is the same as in the case of Embodiment A.

[0178] Further, in the case where a silicon-containing DLC film is formed, it is the same as in the case of Embodiment A.

[0179] When forming a SiO film (silicon oxide film), for example, a mixed gas of silane and oxygen, Alternatively, a mixed gas of HMDSO and oxygen is used as the source gas.

[0180] The vacuum pump 23 exhausts the internal gas of the vacuum chamber 7C. That is, one end of the pipe 21 is connected to the exhaust chamber 5, the other end of the pipe 21 is connected to the vacuum valve 22, and the vacuum valve 22 is connected to the vacuum pump 23 via the pipe. This vacuum pump 23 is further connected to an exhaust duct 24. A pressure gauge 20 is connected to the pipe 21 to detect the pressure in the exhaust path. By operating the vacuum pump 23, the internal gas of the plastic container 8 and the internal gas of the internal space 30C of the reaction chamber 3C move to the internal space 31 of the exhaust chamber 5 through the openings 32a and 32b. The internal gas is sent to the vacuum pump 23 through the exhaust path including the pipe 21.

[0181] The vacuum chamber 7C is connected to a leak pipe 17, and the pipe 17 is connected to a leak source 19 (open to the atmosphere) via a vacuum valve 18.

[0182] The low-frequency power supply means 350 supplies the low-frequency power to the reaction chamber 3C to turn the raw material gas inside the plastic container 8 into plasma. The low-frequency power supply means 350 includes a low-frequency power source 270 and an automatic matching device 260 connected to the low-frequency power source 270, and the low-frequency power source 270 is connected to the reaction chamber 3C via the automatic matching device 260. . The low-frequency power generated by the low-frequency power source 270 is applied between the raw material gas supply pipe 9 (internal electrode) and the reaction chamber 3C (external electrode), so that the raw material gas supplied into the plastic container 8 is Zuma. The frequency of the low frequency power supply 270 is preferably 100 kHz to 3 MHz. If the frequency of the low-frequency power supply 270 exceeds 3 MHz, it will be difficult to generate plasma only in the internal space 30C of the reaction chamber 3C. On the other hand, if the frequency of the low frequency power supply 270 is less than lOOkHz, it may be difficult to discharge.

Next, the principle by which the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed when low frequency power is supplied to the reaction chamber 3C will be described. Figure 2 shows a bipolar discharge-type circuit corresponding to the plasma CVD film-forming system of the first form (C). The AC power supply in the circuit shown in Fig. 2 corresponds to the low-frequency power supply 270. C is the internal space of plastic container 8 and reaction chamber 3C

1

It represents the combined capacitance with 30C. C can be measured by connecting an LCR meter to the plastic container 8 and the reaction chamber 3C. An LCR meter is a device that can measure inductance (L), capacitance (C), resistance (R), and the like. C is insulation It represents the combined capacitance of the body spacer 4C and the internal space 31 of the exhaust chamber 5. C is

2 It can be measured by connecting an LCR meter to the insulator spacer 4C and the exhaust chamber 5.

Z represents the impedance of the plasma generated in the reaction chamber 3C, and Z is pi p2 in the exhaust chamber 5.

Represents the impedance of the plasma generated in In the circuit of Figure 2, Z and Z

Each side of pi p2 represents a sheath. If the current flowing through the entire circuit is I, the current flowing through the C side is I, and the current flowing through the C side is I, then the relationship 1 = 1 + 1 holds. here,

1 2 2 1 2

The impedance A of C is given by Equation 15. The impedance B of C is

1 2

As shown. Where f is the low frequency.

(Equation 15) Impedance A = 1 / (2 π Κ)

1

(Equation 16) Impedance B = lZ (2 fC)

2

[0184] The film deposition system 100C in Fig. 10 is designed so that the relationship C> C is established.

1 2

Is preferred. If the inner space 30C of the reaction chamber 3C is substantially in contact with the outer surface of the plastic container 8, its size is limited by the shape of the plastic container 8, but the inner space 31 or insulator of the exhaust chamber 5 is limited. The material and thickness of the spacer 4C can be changed freely. Therefore, in order to establish the relationship of C> C in advance, for example, insulator spacer 4

1 2

Increase the thickness of C, or make the insulator spacer 4C with a low relative dielectric constant, or make the device to increase the capacity of the internal space 31 of the exhaust chamber 5. deep. Consider the case where 400 kHz low frequency power is output from the low frequency power supply 270. In the film forming apparatus 100C of FIG. 10, the relationship C> C, preferably the relationship C >> C,

1 2 1 2

By designing so as to hold, impedance B can be relatively increased with impedance A as a reference, as shown in Eq. At this time, the generation of plasma in the internal space 30 C of the reaction chamber 3 C is left as it is, and only the generation of plasma in the internal space 31 of the exhaust chamber 5 can be suppressed. And I shown in Fig. 2 can be increased.

1

(Equation 17) Impedance B / Impedance A = C / C

(f = 400kHz) (f = 400kHz) 1 2

[0185] On the other hand, the result of Expression 18 is obtained from Expression 15 and Expression 16. According to Eq. 18, the difference (impedance B—impedance A) is f force M, and when C-C is positive, that is, C> C

It can be seen that it increases only when the 1 2 1 2 relationship holds. c Standing, front

1>> c

2

The difference becomes larger. (Equation 18) Impedance B—Impedance Α = 1/2 π {(C — C) / CC}

1 2 1 2

[0186] In the film forming apparatus 100C of FIG. 10, the relationship C> C, preferably the relationship C>> C holds.

1 2 1 2

By supplying low frequency power as a source gas plasma energy source, impedance B is relatively increased with reference to impedance A, leading to the exhaust chamber and further to the vacuum pump 23 thereafter. Suppresses the generation of plasma in the exhaust path. As a result, damage due to plasma attack in the exhaust chamber and exhaust path can be reduced, and the amount of dust in the source gas system can be reduced. However, it was found that when the source gas was turned into plasma with low-frequency power, the ignitability or sustainability of the plasma was worse than when the source gas was turned into plasma with high-frequency power. Therefore, in the present embodiment, the spark generating part 40 is disposed inside the plastic container 8 to ensure the plasma ignitability or its sustainability. At this time, it is preferable that the spark generating portion 40 is disposed below the center of the height of the plastic container 8. It is easy to form a gas barrier thin film on the bottom of the container and immediately homogenize the film thickness distribution.

[0187] The plasma CVD film forming apparatus according to the present embodiment is provided with plasma ignition means having the spark generating section 40 based on the configuration described above. The plasma ignition means (idanator unit) having the spark generating section 40 has a plurality of forms, and the plasma CVD film forming apparatus 100C of the first form (C) is provided with a DC ignition type plasma ignition means. Yes.

[0188] In the plasma CVD film forming apparatus 100C, the plasma ignition means has a high-voltage DC power supply 290, and the spark generating unit 40 includes a spark electrode connected to the high-voltage DC power supply 290 and a ground electrode that is opposed to the spark electrode. And a spark is generated between the spark electrode and the ground electrode. The spark electrode and the ground electrode are separated by 2 to 5 mm, for example. The high-voltage DC power supply 290 is preferably a DC high-voltage power supply of about 1 to:! Spark is generated in the plastic container 8 by applying a voltage to the spark electrode. The spark may be generated at least for the time required for the plasma to ignite, but may be continuously generated throughout the film formation time. This spark assists the ignition of the plasma.

[0189] In the plasma CVD film forming apparatus 100C of the first embodiment (C), the source gas supply pipe 9 is formed of a conductive material, and a linear or rod-like conductor 41 is placed in the pipe at the tip. Removal And a gas channel 43 that is housed in a state of being covered with an insulator 42 and that blows a source gas to the tip of the conductor 41. Here, the conductor 41 is a spark electrode, and the source gas supply pipe 9 is a ground electrode. The ground electrode serves as the counter electrode | J (internal electrode) of reaction chamber 3C, which is the external electrode. The on / off of the high-voltage DC power supply 290 is switched by the switch 280.

[0190] Since the conductor 41 becomes a spark electrode, the conductor 41 is made of molybdenum, tantalum, zirconium, niobium, nickel, iridium, platinum, a base alloy of these metals, or carbon fiber. Is preferred. It is possible to suppress electrode consumption and contamination of the electrode material into the container. Further, if the electrode material is carbon fiber, there is no fear of electrode material contamination when a carbon film is formed as a gas barrier thin film.

[0191] Another type of film forming apparatus provided with a DC discharge type plasma ignition means is a plasma CVD film forming apparatus 200C of the second mode (C) shown in FIG. FIG. 13 shows a diagram for explaining the details of FIG. Here, FIG. 13 (a) is a BB cross-sectional view, and FIG. 13 (b) is a partially enlarged schematic view of the spark generating portion 40. In this film forming apparatus 200C, the source gas supply pipe 9 is formed of a conductive material and is covered with an insulator 42 except for the tip thereof, and the source gas supply pipe 9 is used as an inner pipe. An outer tube 44 made of a conductive material is disposed outside the structure to form a double tube structure. The outer tube 44 is a ground electrode, and the source gas supply tube 9 is a spark electrode. The ground electrode serves as the counter electrode (internal electrode) of the reaction chamber 3C that serves as the external electrode. The on / off of the high-voltage DC power supply 290 is switched by the switch 280.

[0192] Since the source gas supply pipe 9 serves as a spark electrode, the same material as in the case of the plasma CVD film forming apparatus 100C is selected.

[0193] Next, the case where the plasma ignition means having the spark generating unit 40 is a low-frequency discharge method will be described by showing two embodiments of the film forming apparatus. First, there is a plasma CVD film forming apparatus 300C of the third embodiment shown in FIG. In FIG. 14, an AA cross-sectional view and a partially enlarged schematic view of the spark generating portion 40 are as shown in FIG.

[0194] In FIG. 14, in the plasma CVD film forming apparatus 300C, the plasma ignition means has a distributor 250 connected to the low-frequency power supply means 350, and the spark generator 40 has a distributor 250. A spark electrode and a ground electrode opposite to the spark electrode, and generates a spark between the spark electrode and the ground electrode. The spark electrode and the ground electrode are separated by 2-5 mm, for example. As the energy source for generating sparks, the low frequency power supply means 350 of the low frequency power supply means 350 is also used. Another low frequency power supply may be connected. Spark is generated inside the plastic container 8 by applying low-frequency power to the spark generator 40. The on / off of the supply of the low-frequency power to the spark generator 40 is switched by the switch 280. The spark is generated through the film formation time. The supply of low-frequency power to the spark generation unit 40 is stopped by the force switch 280, and plasma is generated at least for the time required for the plasma to ignite. As good as it is. This spark assists the ignition of the plasma. A phase shifter 45 is preferably connected in series between the distributor 250 and the spark electrode. This increases the sustainability of the low frequency discharge. The plasma CVD film forming apparatus 300C of the third form (C) has the source gas supply pipe 9 having the same structure as the film forming apparatus 100C of the first form (C), and the source gas supply pipe 9 is grounded. The conductor 41 is a spark electrode. The material for the spark electrode is selected in the same way.

[0195] Another form of film forming apparatus provided with a low-frequency discharge type plasma ignition means is a plasma CVD film forming apparatus 400C shown in FIG. In FIG. 15, a BB cross-sectional view and a partial enlarged schematic view of the spark generating portion 40 are as shown in FIG. In the film forming apparatus 400C, low-frequency power is supplied to the spark generating unit 40 in the same manner as the film forming apparatus 300C shown in FIG. In addition, a source gas supply pipe having the same structure as that of the source gas supply pipe 9 of the film forming apparatus 200C shown in FIG. 12 is provided, and the outer pipe 44 is a ground electrode and the source gas supply pipe 9 is a spark electrode. . The material for the spark electrode is selected in the same manner.

[0196] In any of the first to fourth embodiments, the insulator 42 is preferably an insulator.

[0197] Foreign materials derived from the source gas may adhere to the surface of the source gas supply pipe 9, which becomes a spark electrode or a ground electrode, the tip of the conductor 41, and the surface of the outer pipe 44. In order to remove this, wiping means can be provided for wiping, or energization means can be provided to generate heat and burn. It is derived from source gas such as carbon-based foreign matter on the spark electrode or ground electrode Since foreign matter can be removed even if it deposits, it is possible to reduce the outage caused by electrode cleaning.

Next, a method for manufacturing a gas barrier plastic container according to this embodiment will be described. Unless otherwise specified, the case where a DLC film is formed as a gas barrier thin film using the film forming apparatus 100C of FIG. 10 will be described.

[0199] The vacuum chamber 7C is opened to the atmosphere by opening the vacuum valve 18, and the lower external electrode 1 of the reaction chamber 3C is removed from the upper external electrode 2. A plastic container 8 is inserted into the space inside the upper external electrode 2 from the lower side of the upper external electrode 2 and installed in the internal space 30C of the reaction chamber 3C. At this time, the source gas supply pipe 9 is inserted into the plastic container 8. Next, the lower external electrode 1 is attached to the lower part of the upper external electrode 2, and the reaction chamber 3 C is sealed with a ring 10.

[0200] Next, the inside of the plastic container 8 is replaced with a raw material gas and adjusted to a predetermined film forming pressure. That is, as shown in FIG. 10, after the vacuum valve 18 is closed, the vacuum valve 22 is opened, the vacuum pump 23 is operated, and the gas in the reaction chamber 3C is electrically connected to the reaction chamber 3C by the insulator spacer 4C. Exhaust through the electrically insulated exhaust chamber 5. As a result, the inside of the vacuum chamber 7C including the inside of the plastic container 8 is exhausted through the pipe 21, and the inside of the vacuum chamber 7C is evacuated. The pressure in the vacuum chamber 7C at this time is 2.6 to 66 Pa, for example. Next, the vacuum valve 12 is opened, a hydrocarbon gas such as acetylene gas is generated in the source gas generation source 15, this hydrocarbon gas is introduced into the pipe 14, and the hydrocarbon gas whose flow rate is controlled by the mass flow controller 13. Is blown out from the gas outlet 9a through the pipe 11 and the source gas supply pipe (internal electrode) 9 at ground potential. As a result, hydrocarbon gas is introduced into the plastic container 8. The vacuum chamber 7 C and the plastic container 8 are maintained at a pressure suitable for the formation of the DLC film (for example, about 6.6 to 665 Pa) and stabilized by controlling the balance between the gas flow rate and the exhaust capacity. Let

[0201] Next, when the raw material gas is blown into the plastic container 8 under a predetermined reduced pressure, low frequency power (eg, 400 kHz) is supplied to the reaction chamber 3C. The raw material gas in the plastic container 8 is turned into plasma using low frequency power as an energy source. As a result, a DLC film is formed on the inner surface of the plastic container 8. In other words, reaction chamber 3C By supplying the low frequency power, a bias voltage is generated between the reaction chamber 3C and the raw material gas supply pipe 9, and the raw material gas in the plastic container 8 is turned into plasma to generate hydrocarbon-based plasma. A film is formed on the inner surface of the plastic container 8. At this time, the automatic matching device 260 matches the impedance by the inductance recapacitance C so that the reflected wave from the entire electrode supplying the output is minimized.

[0202] Switch 280 is turned on almost simultaneously with the supply of low-frequency power. As a result, the plasma ignition means is activated, and the spark generating part 40 is connected to the conductor 41 (spark electrode) and grounded, and sparks are generated between the source gas supply pipe 9 and the DC gas discharge. Thereby, when the raw material gas is turned into plasma using low frequency power as an energy source, ignition failure is reduced and ignition sustainability is imparted. The presence or absence of ignition is determined by detection means (not shown) such as an ignition monitor. The spark may be stopped immediately after the plasma is ignited.

[0203] In the film forming apparatus 100C of FIG. 10, the relationship C> C, preferably the relationship C>> C,

1 2 1 2 By supplying low-frequency power in the established state, as explained in FIG. 2 and Equations 15 to 18, in the exhaust path to the exhaust chamber 5 and then to the vacuum pump 23, Plasma generation can be suppressed. As a result, damage caused by plasma attack in the exhaust chamber 5 and the exhaust path can be reduced, and the amount of dust in the source gas system can be reduced. Here, as the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed, energy is consumed for the generation of plasma in the internal space 30C of the reaction chamber 3C. When the center where the plasma is generated is the part from the shoulder to the mouth of the plastic container 8, it moves to the trunk which is the center of the plastic container 8. Therefore, the film thickness distribution along the main axis direction of the container is made uniform.

[0204] By making the film thickness distribution uniform, the film thickness of the DLC film on the inner wall of the mouth of the plastic container 8 becomes thinner compared to the conventional one. The resulting coloration is reduced and the design is improved.

Next, the output of the low frequency power from the low frequency power supply 270 is stopped, the plasma is extinguished, and the film formation of the DLC film is completed. At about the same time, the vacuum valve 12 is closed and the supply of the raw material gas is stopped.

[0206] Next, the hydrocarbon gas remaining in the vacuum chamber 7C and the plastic container 8 is removed. Therefore, the vacuum pump 23 exhausts the air. After that, the vacuum valve 22 is closed and the exhaust is finished. At this time, the pressure in the vacuum chamber 7C is 6.6 to 665 Pa. After this, the vacuum valve 18 is opened. Thereby, the vacuum chamber 7C is opened to the atmosphere.

[0207] In either case, the film formation time is as short as several seconds. The DLC film is formed to a thickness of 0.003 to 5 μm.

[0208] When the film forming apparatus 200C of Fig. 12 is used, the switch 280 is turned on at the same time as the supply of the low frequency power. As a result, the plasma ignition means is activated, and a spark is generated by a direct current discharge between the source gas supply pipe 9 as a spark electrode and the outer pipe 44 as a ground electrode in the spark generation section 40. As a result, when the raw material gas is turned into plasma using low frequency power as an energy source, ignition failure is reduced and ignition sustainability is imparted. The presence or absence of ignition is determined by detection means (not shown) such as an ignition monitor. The spark may be stopped immediately after the plasma is ignited.

[0209] When the film forming apparatus 300C of Fig. 14 is used, the switch 280 is turned on at the same time as the supply of the low frequency power. As a result, the plasma ignition means is activated, and a spark due to the low frequency discharge is generated between the conductor 41 as the spark electrode and the source gas supply pipe 9 as the ground electrode in the spark generator 40. As a result, when the raw material gas is turned into plasma using low-frequency power as an energy source, ignition failure is reduced and ignition sustainability is imparted. Presence or absence of ignition is determined by detection means (not shown) such as an ignition monitor. The spark may be stopped immediately after the plasma is ignited.

[0210] When the film forming apparatus 400C of Fig. 15 is used, the switch 280 is turned on at the same time as the supply of the low-frequency power. As a result, the plasma ignition means is activated, and a spark is generated by the low frequency discharge between the source gas supply tube 9 as the spark electrode and the outer tube 44 as the ground electrode in the spark generation unit 40. As a result, when the raw material gas is turned into plasma using low frequency power as an energy source, ignition failure is reduced and ignition sustainability is imparted. Presence or absence of ignition is determined by detection means (not shown) such as an ignition monitor. The spark may be stopped immediately after the plasma is ignited.

Example

[0211] (Embodiment A) Hereinafter, the present invention will be described in more detail with reference to examples. The plastic container used in the examples has a capacity of 500 ml, a container height of 207 mm, a container monthly diameter of 68 mm, a mouth opening inner diameter of 21.74 mm, a mouth opening outer diameter of 24.94 mm, and a mouth height. 21. This is a round PET (polyethylene terephthalate) bottle with Omm, container body thickness of 0.3mm, and resin amount of 30g / piece.

[0212] Evaluation was performed as follows.

(Film uniformity)

The film formation uniformity was determined as follows. Measure the film thickness at 3 locations in the circumferential direction, 2cm above (bottom), 8cm above (trunk), and 16cm above (shoulder) above the bottom of the container. The film thickness was measured with a stylus type step gauge of Tenchol alpha_step500. By averaging them, the average film thickness of the bottom, the trunk and the shoulder is obtained. From the average film thickness at the bottom, torso and shoulder, select the result with the largest average film thickness (average film thickness A) and the result with the smallest average film thickness (average film thickness B). Obtain film formation uniformity (%). The lower the deposition uniformity (%), the higher the uniformity.

(Equation 5) Film uniformity (%) = (Average film thickness A—Average film thickness B) / (Average film thickness A + Average film thickness B) X 100

Uniformity of film formation 15% or less: (◯) Good film formation in the container height direction. Uniformity of film formation Over 15% and 30% or less: (△) There is no problem in quality because the film is formed uniformly in the container height direction.

Uniformity of film formation> 30%: (X) It can be visually observed that there is unevenness in the container height direction.

[0213] (Deposition rate)

By dividing the average film thickness A of the container by the film formation time, the film thickness per unit time (second) was obtained.

Deposition rate lOnmZ seconds or more: (◯) Good production efficiency.

Deposition rate less than lOnmZ seconds: (X) There is a problem because the production efficiency is lowered.

[0214] (Light emission in exhaust chamber)

In order to investigate the presence and extent of plasma generation in the internal space of the exhaust chamber, one end (light incident part) of the optical fiber is installed in the internal space and the other end of the optical fiber is connected to a discharge sensor (photo diode, (Yamatake photoelectric sensor, HPX-MA-063) The light incident on the optical fiber was monitored. The position of the light incident portion of the optical fiber is, for example, the location indicated by “D” in the film forming apparatus of FIG. The presence or absence and degree of plasma generation in the exhaust chamber were evaluated based on the output value (V) of the discharge sensor. The larger the output value, the greater the amount of plasma generated in the exhaust chamber.

Luminous emission 0.3 V or less: (○) No generation of plasma in the exhaust chamber and good continuous operation for a long time.

Amount of emitted light: More than 0.3 V and 0.5 V or less: (△) Plasma is slightly generated in the exhaust chamber, but this is a problem in continuous operation for a long time.

Emission amount> 0.5V: (X) Plasma is generated in the exhaust chamber, causing problems in continuous operation for a long time.

[0215] (Amount of foreign matter generated in the exhaust chamber)

Silicon chip A is attached to the wall surface of the opening 32b (for example, the location indicated as E in FIG. 1), and silicon chip B is attached to the wall surface near the exhaust port of the exhaust chamber 5 (eg, the location indicated as F in FIG. 1). The film was formed in a container 20 times under the same conditions, and then taken out and weighed with an electronic balance (manufactured by Shinko Denshi, high-precision electronic balance AF-R220). The amount of adhering foreign matter was determined from the weight difference before and after film formation.

Amount of adhering foreign matter 0.2 mg or less: (○) Good for long-term continuous operation with almost no foreign matter adhering.

Amount of adhering foreign matter More than 0.2 mg 0.4 mg or less: (△) Foreign matter adhering slightly, but no problem in continuous operation for a long time.

Amount of adhering foreign matter> 0.4 mg: (X) There is a foreign matter adhering, causing problems in continuous operation for a long time.

[0216] (Oxygen permeability of PET bottle)

Oxygen permeability is 22 ° CX 60 with Oxtran manufactured by Modern Control. /. Measurement was performed one week after the start of measurement under the RH conditions. In the present invention, the oxygen permeability (oxygen barrier property) is calculated per container. When this is converted per area (m ² ), it may be converted in consideration of the inner surface area of the container. Since there is almost no gas permeation from the mouth lid, the area is not taken into consideration.

Oxygen permeability 0.005ml Z day Below Z container: (◎) Oxygen barrier property is sufficiently good and oxygen Can be used for sensitive beverages.

Oxygen permeability 0.005ml / day / over container 0.010ml / day / container or less: (○) Oxygen-free, good for oxygen-sensitive beverages.

Oxygen permeability 0. OlOmlZ day Z container over 0.015ml Z day Z container or less: (△) Can be used as a simple oxygen barrier container without any problems.

Oxygen permeability 0.015ml Z day Over Z container: (X) There is a problem as an oxygen barrier container.

[0217] (Exam 1)

Using the gas barrier plastic container manufacturing apparatus 100A shown in Fig. 1, a DLC film was formed on the inner wall of the PET bottle. The film forming conditions are as follows: acetylene is used as the source gas, the source gas flow rate is 120 sccm, the volume of the internal space 31 of the exhaust chamber 5 is 1.2 liters, and the thickness of the insulating member 4 (made of polyester ether ketone) is set. The output of 10 mm, power supply 27 (3. OMHz) was 600 W, and the film formation time was 2 seconds. In addition, an outer electrode 3 having an inner space 30 having a cylindrical shape was used, and a spacer 36 made of polyetheretherketone was installed in a gap space when the PET bottle was inserted. The inner diameter of the cylindrical shape of the inner space 30 is such that the outer wall surface of the body of the PET bottle and the inner wall surface of the inner space 30 are substantially in contact with each other. As shown in Fig. 1, the combined capacitance of the PET bottle 8 and the inner space 30 of the outer electrode 3 is C, and the combined capacitance of the insulating member 4 and the inner space 31 of the exhaust chamber 5 is C. When C> C, the relationship was established. Generation of foreign matter

2 1 2

The amount was evaluated after film formation 20 times under these conditions. Exhaust chamber 5 emitted a slight amount of light at 0.4V. The amount of foreign matter generated (A) was 0.3 mg, and (B) was 0.3 mg. It was found that the generation of plasma in the internal space 31 of the exhaust chamber 5 was slight. No abnormal discharge occurred in the gap space between the inner wall surface of the external electrode 3 and the outer wall surface of the PET bottle 8. The film formation uniformity was 18% and the film formation rate was 14 nmZ seconds. Table 1 shows the deposition conditions and results.

[0218] (Exam 2)

A DLC film was deposited on the inner wall of the PET bottle as in Test 1, except that the low frequency was 1. OMHz. The results are shown in Table 1.

[0219] (Exam 3)

A DLC film was deposited on the inner wall of the PET bottle in the same manner as in Test 2 except that the raw material gas flow rate was 80 sccm. The results are shown in Table 1. [0220] (Exam 4)

A DLC film was deposited on the inner wall of the PET bottle as in Test 1, except that the low frequency was 0.4 MHz. The results are shown in Table 1.

[0221] (Exam 5)

A DLC film was deposited on the inner wall of the PET bottle in the same manner as in Test 1, except that a high-frequency power supply (frequency 13.56 MHz) was used instead of the low-frequency power supply. The results are shown in Table 1.

[0222] (Exam 6)

A DLC film was deposited on the inner wall of the PET bottle as in Test 1, except that the low frequency was 0.1 MHz. The results are shown in Table 1.

[0223] (Exam 7)

A DLC film was formed on the inner wall of the PET bottle in the same way as in Test 2 except that the spacer 36 made of polyetheretherketone was not used. The results are shown in Table 1.

[0224] (Exam 8)

Capacity 480ml, container height 207mm, container month diameter 68mm, mouth opening inner diameter 21.74mm, mouth opening outer diameter 24.94mm, mouth height 21.Omm, container body thickness 0.3mm, resin amount 30g / bottle, round neck PET bottle with the same shape as the polyether ether ketone spacer 36 except for the use of DLC on the inner wall of the PET bottle as in Test 2 A film was formed. The results are shown in Table 1.

[0225] (Exam 9)

The oxygen permeability of uncoated PET bottles was measured. The results are shown in Table 1.

[0226] (Exam 10)

Instead of the gas barrier plastic container manufacturing equipment 100A shown in Fig. 1, C <C

Using the equipment in which the relationship of 1 and 2 was established, the film was formed under the same conditions as in Test 2 except for the above. Table 1 shows the deposition conditions and results.

[0227] In Table 1, the overall evaluation is described. Judgment materials were the presence / absence of abnormal discharge, the amount of luminescence, the amount of attached foreign matter, the deposition rate, deposition uniformity, and oxygen barrier properties. Of these, tests that included an evaluation of X or tests in which abnormal discharge occurred were judged as comprehensive evaluation X. In addition, in the tests other than the comprehensive judgment X, any test that includes an evaluation of △ The price was judged to be △. A test that obtained an evaluation of ◯ or ◎ was judged as an overall evaluation ◯. The test judged as comprehensive evaluation Δ or ○ has the characteristics of the above evaluation items in a well-balanced manner.

[table 1]

*: Can be evaluated because of film thickness

[0229] The PET bottle coated with the thin film having gas barrier properties obtained in Tests 1 to 4 had oxygen barrier properties and suppressed generation of plasma in the exhaust chamber. Abnormal discharge was suppressed by the spacer made of polyetheretherketone. In addition, there was little unevenness in film formation in the height direction of the container. Furthermore, in Test 8, it was found that PET bottles with different shapes can be similarly formed without causing abnormal discharge. Therefore, it was found that the cleaning work time for removing foreign substances and the external electrode replacement work time can be reduced, and as a result, the production efficiency of the film forming apparatus can be maintained high.

[0230] On the other hand, in Test 5, since a high-frequency power supply was used, a bottle with good oxygen-nore properties was obtained, but plasma generation in the exhaust chamber was significant, and cleaning work was performed to remove foreign matter. This takes time and causes the production efficiency of the film forming apparatus to drop. In addition, there was uneven film formation in the height direction of the container.

[0231] In Test 6, since the frequency was as low as 0.1 MHz, the generation of plasma in the exhaust chamber was suppressed, but the deposition rate was slow and the oxygen barrier property was low.

[0232] In addition, in Test 7, since the force was not applied using the spacer, plasma was generated as an abnormal discharge in the gap space, and excessive power was consumed in that portion, resulting in a decrease in film formation uniformity. It was. As a result, the oxygen barrier property decreased from 0.006 ml / day / container (Test 2) to 0.008 ml / day / container (Test 7) compared to no spacer (Test 2). In addition, carbon-based foreign matter adhered to the inner wall of the external electrode, and dust was observed as the operation continued. Periodic cleaning work is required due to the generation of dust.

[0233] In Test 10, since the relationship of C <C is established, carbon-based foreign matter is detected on the inner wall surface of the exhaust chamber.

1 2

As a result, the generation of dust was observed with continuous operation. Periodic cleaning work is required due to the generation of dust. In addition, since plasma was generated in the exhaust chamber, the deposition rate was low.

[0234] (Embodiment B)

Hereinafter, the present invention will be described in more detail with reference to examples. The plastic container used in the examples has a capacity of 500 ml, a container height of 207 mm, a container body diameter of 68 mm, a mouth opening inner diameter of 21.74 mm, a mouth opening outer diameter of 24.94 mm, and a mouth height of 21. It is a PET (polyethylene terephthalate) container with Omm, container body thickness of 0.3 mm, and resin amount of 30 g / bottle. [0235] The evaluation was performed as follows.

(Film uniformity)

The film formation uniformity was determined as follows. Measure the film thickness at 3 locations in the circumferential direction, 2cm above (bottom), 8cm above (trunk), and 16cm above (shoulder) above the bottom of the container. The film thickness was measured with a stylus type step gauge of Tenchol alpha_step500. By averaging them, the average film thickness of the bottom, the trunk and the shoulder is obtained. From the average film thickness of the bottom, trunk, and shoulder, the average film thickness is the result of the thick layer (average film thickness A) and the thinnest average film thickness is the result (average film thickness B). The film formation uniformity (%) is obtained by Equation 14. The lower the deposition uniformity (%), the higher the uniformity.

(Equation 14) Film formation uniformity (%) = (Average film thickness A—Average film thickness B) / (Average film thickness A + Average film thickness B) X 100

[0236] (Deposition rate)

[0237] (Light emission in exhaust chamber)

In order to investigate the presence and extent of plasma generation in the internal space of the exhaust chamber, one end of the optical fiber (light incident part) is installed in the internal space, and the other end of the optical fiber is connected to a discharge sensor (photo diode, Connected to a Yamatake photoelectric sensor, HPX-MA-063), the light incident on the optical fiber was monitored. The position of the light incident part of the optical fiber is, for example, the location indicated by “D” in the manufacturing apparatus of FIG. The presence or absence and degree of plasma generation in the exhaust chamber were evaluated based on the output value (V) of the discharge sensor. The larger the output value, the greater the amount of plasma generated in the exhaust chamber.

[0238] (Dust generation amount in the exhaust chamber)

Silicon chip A is attached to the wall surface of the opening 32b (for example, the location indicated as E in FIG. 4), and silicon chip B is attached to the wall surface near the exhaust port of the exhaust chamber 5 (eg, the location indicated as F in FIG. 4). After depositing the film in the container 20 times under the same conditions, it was taken out and weighed with an electronic balance (manufactured by Shinko Denshi, high-precision electronic balance AF-R220). The amount of adhering dust was determined from the difference in weight before and after film formation. [0239] (Exam 1)

Using the gas barrier plastic container manufacturing apparatus 100B shown in Fig. 4, a DLC film was deposited on the inner wall of the PET bottle. The deposition conditions are: acetylene is used as the source gas, the source gas flow rate is 120 sccm, the volume of the internal space 31 in the exhaust chamber 5 is 1.2 litter, and the thickness of the insulator spacer 4B (made of polyetheretherketone). The output of the high-frequency power supply 29 (13. 56 MHz) is 600 W, the output of the low-frequency power supply 270 (0.4 MHz) is 0 W, and the deposition time is 2 seconds. The amount of dust generated was evaluated after film formation 20 times under these conditions. The evaluation results are shown in Table 2.

[Table 2]

[0240] (Exam 2)

Film formation was performed under the same conditions as in Test 1 except that the output of the high frequency power supply was 500 W and the output of the low frequency power supply was 100 W. The total output of the high-frequency power supply and low-frequency power supply is 600W (the same applies to the following tests). The results are shown in Table 2.

[0241] (Trial 3)

Film formation was performed under the same conditions as in Test 1 except that the output of the high frequency power supply was 400 W and the output of the low frequency power supply was 200 W. The results are shown in Table 2.

[0242] (Exam 4)

Same as Test 1 except the output of the high frequency power supply is 200W and the output of the low frequency power supply is 400W Film formation was performed under the conditions. The results are shown in Table 2.

[0243] (Exam 5)

Film formation was performed under the same conditions as in Test 1 except that the output of the high frequency power supply was 100 W and the output of the low frequency power supply was 500 W. The results are shown in Table 2.

[0244] (Exam 6)

Film formation was performed under the same conditions as in Test 1 except that the output of the high frequency power supply was 400 W, the output of the low frequency power supply was 200 W, and the frequency of the low frequency power supply was 0.1 MHz. The results are shown in Table 2.

[0245] (Exam 7)

Film formation was performed under the same conditions as in Test 6 except that the output of the high frequency power supply was 200 W and the output of the low frequency power supply was 400 W. The results are shown in Table 2.

[0246] (Exam 8)

Film formation was performed under the same conditions as in Test 1 except that the output of the high frequency power supply was 400 W, the output of the low frequency power supply was 200 W, and the frequency of the low frequency power supply was 1 MHz. The results are shown in Table 2.

[0247] (Exam 9)

Film formation was performed under the same conditions as in Test 8 except that the output of the high frequency power supply was 200 W and the output of the low frequency power supply was 400 W. The results are shown in Table 2.

[0248] (Exam 10)

Film formation was performed under the same conditions as in Test 1 except that the output of the high frequency power supply was 400 W, the output of the low frequency power supply was 200 W, and the frequency of the low frequency power supply was 3 MHz. The results are shown in Table 2.

[0249] (Exam 11)

Film formation was performed under the same conditions as in Test 10 except that the output of the high frequency power supply was 200 W and the output of the low frequency power supply was 400 W. The results are shown in Table 2.

[0250] (Exam 12)

Using the gas barrier plastic container manufacturing device 200B shown in Fig. 5, a DLC film was formed on the inner wall of the PET bottle. The deposition conditions are acetylene as the source gas, the source gas flow rate is 120 sccm, the volume of the internal space 31 in the exhaust chamber 5 is 3.6 litter, the thickness of the insulator spacer 4B is 10 mm, and the high frequency power supply (13 The output of 56 MHz) was 600 W and the film formation time was 2 seconds. The amount of dust generated was evaluated after film formation 20 times under these conditions. Comment The results are shown in Table 2.

[0251] (Exam 13)

Film formation was performed under the same conditions as in Test 12, except that the volume of the internal space 31 of the exhaust chamber 5 was changed to 4.8 liters. The evaluation results are shown in Table 2.

[0252] (Exam 14)

Using the gas barrier plastic container manufacturing device 300B shown in Fig. 6, a DLC film was deposited on the inner wall of the PET bottle. The deposition conditions were as follows: acetylene was used as the source gas, the source gas flow rate was 120 sccm, the volume of the internal space 31 of the exhaust chamber 5 was 1.2 liters, the thickness of the insulator spacer 4B was 40 mm, and a high frequency power source (13 The output of 56 MHz) was 600 W and the film formation time was 2 seconds. Note that the amount of dust generated was evaluated after film formation 20 times under these conditions. The evaluation results are shown in Table 2.

[0253] (Exam 15)

Using the gas barrier plastic container manufacturing device 400B shown in Fig. 7, a DLC film was deposited on the inner wall of the PET bottle. A variable capacitor 70 is connected. The deposition conditions are: acetylene is used as the source gas, the source gas flow rate is 120 sccm, the volume of the internal space 31 of the exhaust chamber 5 is 1.2 liters, the thickness of the insulator spacer 4B is 10 mm, and the high frequency power supply 29 The output of (13 · 56 MHz) was 600 W, the film formation time was 2 seconds, and the capacitance of the variable capacitor 70 was 50 pF. The amount of dust generated was evaluated after film formation 20 times under these conditions. The evaluation results are shown in Table 2.

[0254] (Exam 16)

Film formation was performed under the same conditions as in Test 15 except that the capacitance of the variable capacitor 70 was set to 105 pF. The evaluation results are shown in Table 2.

[0255] Comparing test 1 (comparative example) in which only high-frequency power was supplied to test 2 to test 11 in which low-frequency power was superimposed on high-frequency power, emission of the exhaust chamber was achieved by superimposing low-frequency power. It was found that the amount was reduced and plasma generation in the exhaust chamber was suppressed. As a result, the amount of dust attached to the exhaust chamber has also been reduced. On the other hand, when the film formation rate was compared between Test 1 and Test 2 to Test 4, the film formation rate increased in Test 2 to Test 4. It can also be seen that the film formation uniformity has also improved. Plasma generation in the reaction chamber by superimposing low frequency power It is thought that the film formation uniformity was improved because the central part of the plasma generation approached the central part of the container.

[0256] Fig. 9 shows a comparison of the appearance images of the bottle (Fig. 9 (b)) formed 100 times under the conditions of Test 1 and the bottle (Fig. 9 (a)) formed 100 times in Test 4. . Test 4 shows that film formation at the container mouth was suppressed. This is probably because the central part of the plasma generation has shifted downward.

[0257] In Test 12 and Test 13 in which the volume of the exhaust chamber 5 was increased, it was found that the amount of luminescence in the exhaust chamber was reduced and plasma generation in the exhaust chamber was suppressed as compared with Test 1. As a result, the amount of dust attached to the exhaust chamber has also been reduced.

[0258] Test 14 in which the thickness of the insulator spacer 4B was increased was found to be less than the test 1 in that the amount of light emitted from the exhaust chamber was reduced and plasma generation in the exhaust chamber was suppressed. As a result, the amount of dust attached to the exhaust chamber has also been reduced.

[0259] When the variable capacitor 70 is connected in series between the exhaust chamber 5 and the ground as shown in Fig. 7, the insulator spacer 4B, the exhaust chamber 5 and the variable capacitor 70 are connected from the reaction chamber 3C. If the impedance of the current path that is grounded is defined as G, the impedance due to the combined capacitance C in the current path is B, and the capacity of the variable capacitor 70 is reduced.

2

In other words, the impedance caused by the combined capacitance C contained in the impedance G

2

B will increase. In Test 15 and Test 16 with the variable capacitor 70 connected, by adjusting the capacity of the variable capacitor 70 in comparison with the impedance A of the synthetic capacitance C between the plastic container 8 and the internal space 30B of the reaction chamber 3B, Since the impedance B was increased, it was found that the amount of light emitted from the exhaust chamber decreased compared to Test 1, and the generation of plasma in the exhaust chamber was suppressed. As a result, the amount of dust attached to the exhaust chamber has also been reduced. In Test 15 and Test 16, Test 15 in which the capacity of the variable capacitor 70 was reduced further suppressed plasma generation in the exhaust chamber.

[0260] (Embodiment C)

Hereinafter, the present invention will be described in more detail with reference to examples. The plastic container used in the examples has a capacity of 500 ml, a container height of 207 mm, a container body diameter of 68 mm, a mouth opening inner diameter of 21.74 mm, a mouth opening outer diameter of 24.94 mm, and a mouth height of 21. A PET (polyethylene terephthalate) container with a thickness of 0.3 mm and a container body thickness of 0.3 mm and a resin amount of 30 g / bottle. [0261] Evaluation was performed as follows.

(Film uniformity)

The film formation uniformity was determined as follows. Measure the film thickness at 3 locations in the circumferential direction, 2cm above (bottom), 8cm above (trunk), and 16cm above (shoulder) above the bottom of the container. The film thickness was measured with a stylus type step gauge of Tenchol alpha_step500. By averaging them, the average film thickness of the bottom, the trunk and the shoulder is obtained. From the average film thickness at the bottom, torso, and shoulder, select the average film thickness results (average film thickness A) and the thinnest average film thickness results (average film thickness B). To obtain the film formation uniformity (%). The lower the deposition uniformity (%), the higher the uniformity.

(Equation 19) Film formation uniformity (%) = (Average film thickness A—Average film thickness B) / (Average film thickness A + Average film thickness B) X 100

[0262] (Deposition rate)

[0263] (Light emission in exhaust chamber)

In order to investigate the presence and extent of plasma generation in the internal space of the exhaust chamber, one end of the optical fiber (light incident part) is installed in the internal space, and the other end of the optical fiber is connected to a discharge sensor (photo diode, Connected to a Yamatake photoelectric sensor, HPX-MA-063), the light incident on the optical fiber was monitored. For example, in the film forming apparatus shown in FIG. 10, the position of the light incident part of the optical fiber is the part indicated by “D”. The presence or absence and degree of plasma generation in the exhaust chamber were evaluated based on the output value (V) of the discharge sensor. The larger the output value, the greater the amount of plasma generated in the exhaust chamber.

[0264] (Dust generation amount in the exhaust chamber)

A silicon chip A is attached to the wall surface of the opening 32b (for example, the location indicated as E in FIG. 10), and the silicon chip B is disposed near the exhaust port of the exhaust chamber 5 (for example, the location indicated as F in FIG. 10). The film was formed in a container 20 times under the same conditions, then taken out and weighed with an electronic balance (manufactured by Shinko Denshi, high-precision electronic balance AF-R220). The amount of dust attached was determined from the difference in weight before and after film formation. [0265] (Exam 1)

Using the plasma CVD film forming apparatus 100C shown in Fig. 10, a DL C film was formed on the inner wall surface of the PET bottle. The deposition conditions are: acetylene is used as the source gas, the source gas flow rate is 120 sccm, the volume of the internal space 31 of the exhaust chamber 5 is 1.2 litter, and the insulator spacer 4C (made of polyetheretherketone) is used. The thickness was 10 mm, the output of the low-frequency power supply 270 (0.4 MHz) was 600 W, and the film formation time was 2 seconds. The plasma ignition means was activated. The amount of dust generated was evaluated after 20 film formations under these conditions. The amount of light emitted from the exhaust chamber 5 was 0V and no light was emitted. The amount of dust generated (A) was 0.1 mg or less, and (B) was 0.1 mg or less, and plasma was generated only in the internal space of the reaction chamber 3C. The film formation uniformity was 8%, and the film formation rate was 143 A / s.

[0266] (Exam 2)

On the other hand, as a comparative example, a plasma CVD film-forming device (not shown) with a high-frequency power supply (13.56 MHz) connected instead of low-frequency power and a source gas supply pipe as an internal electrode was used on the inner wall surface of the PET bottle. A DLC film was formed. The deposition conditions are: acetylene is used as the source gas, the source gas flow rate is 120 sccm, the volume of the internal space of the exhaust chamber is 1.2 liters, the thickness of the insulator spacer (made of polyetheretherketone) is 10 mm, The output of the high frequency power supply (13 · 56MHz) was 600W and the film formation time was 2 seconds. Plasma ignition means are not equipped. The amount of dust generated was evaluated after film formation 20 times under these conditions. The amount of light generated in exhaust chamber 5 is 1 · 8V, the amount of dust generated (A) is 1 · 0mg, and (B) is 0 · 6mg. Both the internal space of reaction chamber 3C and the internal space of exhaust chamber 5 are Plasma was generated. The film formation uniformity was 36% and the film formation rate was 176 A / s.

[0267] When test 2 (comparative example) that supplied high-frequency power was compared with test 1 that supplied low-frequency power, when the low-frequency power was supplied, the amount of light emitted from the exhaust chamber did not emit at 0V, and It was found that the generation of plasma was suppressed. Along with this, the amount of dust attached to the exhaust chamber has also been reduced. It was also found that the film formation uniformity was improved.

[0268] Fig. 16 shows a comparison of the appearance images of a bottle (Fig. 16 (a)) 100 times deposited under the conditions of Test 1 and a bottle (Fig. 16 (b)) 100 times deposited in Test 2. . Test 1 shows that film formation at the container mouth was suppressed. This is probably because the central part of the plasma generation has shifted downward. [0269] (Trial 3)

Under the conditions of Test 1, the plasma ignition means was activated, sparks were always generated at the spark generator 40, and the sparks were extinguished almost simultaneously with the ignition of the plasma. When the number of times of film formation was 30,00 0 times, the plasma non-ignition trouble was 0 times. In the meantime, the tips of the outer surface of the raw material gas supply pipe 9 (inner electrode) and the linear or rod-like conductor 41 as a spark electrode were also cleaned at an appropriate time.

[0270] (Exam 4)

As a comparative example, the film formation was repeated under the conditions of Test 1 without operating the plasma ignition means. When 30,000 depositions were performed, there were 17 plasma non-ignition troubles. In this case as well, the tips of the outer surface of the source gas supply pipe 9 (inner electrode) and the linear or rod-like conductor 41 as the spark electrode were cleaned.

[0271] In Test 4, plasma is generated by supplying low-frequency power. Therefore, considering the results of Test 1, it can be seen that the generation of plasma in the internal space 31 of the exhaust chamber 5 is suppressed. Trouble with poor ignition or poor ignition persistence occurred. On the other hand, in Test 3, the gas barrier plastic container manufactured in Test 1 that eliminates such troubles was stably manufactured.

Claims

The scope of the claims

[1] An external electrode serving as a vacuum chamber that accommodates a plastic container, an internal electrode serving as a source gas supply pipe that is detachably disposed inside the plastic container, and a vacuum that exhausts gas inside the external electrode A pump, a power source connected to the external electrode, an exhaust chamber communicating with the internal space of the external electrode and the opening of the plastic container, and the external electrode and the exhaust chamber are electrically insulated. In an apparatus for producing a gas barrier plastic container, comprising an insulating member, and forming a thin film having a gas barrier property by a plasma CVD method on the inner wall surface of the plastic container.

1

The combined capacitance of the outer space of the plastic container among the inner space of the knit is assumed to be c

2 when c> c holds, and

1 2

The apparatus for producing a gas barrier plastic container, wherein the power supply supplies low frequency power having a frequency of 400 kHz to 4 MHz to the external electrode.

[2] The plastic container has a shape in which the mouth portion has a reduced diameter with respect to the trunk portion,

The external electrode has a cylindrical internal space having an inner diameter slightly larger than the body diameter of the plastic container,

The spacer is disposed in a gap space sandwiched between an outer wall surface of a portion having a reduced diameter from a body portion to a mouth portion of the plastic container and a cylindrical inner wall surface of the external electrode. The apparatus for producing a gas barrier plastic container according to claim 1.

[3] The external electrode has an internal space that accommodates the entire plastic container or an internal space that accommodates the entire plastic container excluding the mouth. An apparatus for producing a gas barrier plastic container as described in 1. above.

[4] storing a plastic container in an external electrode serving as a vacuum chamber;

A step of disposing an internal electrode serving as a source gas supply pipe inside the plastic container; and a gap space sandwiched between an inner wall surface of the external electrode and an outer wall surface of the plastic container. Placing a spacer made of a dielectric;

1

When the combined capacitance of the outer space of the plastic container is C

2

And C> C, the external electrode has a frequency of 400 kHz to 4 MHz.

1 2

A method for producing a gas-barrier plastic container, comprising:

5. The method for producing a gas barrier plastic container according to claim 4, wherein a carbon film, a silicon-containing carbon film, or a SiO film is formed as the gas barrier thin film.