WO2008041386A1 - Dispositif de production d'un contenant de plastique imperméable aux gaz et procédé de production correspondant - Google Patents

Dispositif de production d'un contenant de plastique imperméable aux gaz et procédé de production correspondant Download PDF

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Publication number
WO2008041386A1
WO2008041386A1 PCT/JP2007/058458 JP2007058458W WO2008041386A1 WO 2008041386 A1 WO2008041386 A1 WO 2008041386A1 JP 2007058458 W JP2007058458 W JP 2007058458W WO 2008041386 A1 WO2008041386 A1 WO 2008041386A1
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WO
WIPO (PCT)
Prior art keywords
plastic container
gas
external electrode
frequency power
plasma
Prior art date
Application number
PCT/JP2007/058458
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English (en)
Japanese (ja)
Inventor
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
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Filing date
Publication date
Application filed by Mitsubishi Shoji Plastics Corporation, Youtec Co., Ltd., Kirin Beer Kabushiki Kaisha filed Critical Mitsubishi Shoji Plastics Corporation
Publication of WO2008041386A1 publication Critical patent/WO2008041386A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes

Definitions

  • 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.
  • 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.
  • 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).
  • DLC diamond-like carbon
  • 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.
  • a carbon source gas such as aliphatic hydrocarbons or aromatic hydrocarbons carbon
  • 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.
  • Patent Document 1 Japanese Patent No. 2788412
  • Patent Document 2 Japanese Patent No. 3072269
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the impedance is not determined by the plastic container, the external electrode, and the internal electrode.
  • 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.
  • 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.
  • 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.
  • the apparatus for producing a gas-no plastic plastic container 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.
  • 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
  • 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;
  • 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.
  • C is the combined capacitance of the outer space of the plastic container in the inner space of the knit.
  • the power supply supplies low frequency power having a frequency of 400 kHz to 4 MHz to the external electrode.
  • 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.
  • 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.
  • 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,
  • the external electrode has a frequency of 400 kHz to 4 MHz.
  • 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.
  • 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.
  • 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.
  • the impedance B is relatively increased with the impedance A as a reference to suppress the generation of plasma in the exhaust 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.
  • Impedance B of impedance B of combined capacitance C with subspace is
  • the gas barrier thin film is formed in a relatively high state with respect to the dance A.
  • 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.
  • Impedance B 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.
  • 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.
  • Impedance B can be increased by adjusting the capacitance of the variable capacitor.
  • the frequency of the high frequency power is preferably 13.56 MHz.
  • 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.
  • 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.
  • 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.
  • the apparatus for producing a gas-no plastic plastic container 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
  • 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
  • Impedance B of impedance B of combined capacitance C with subspace is
  • 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.
  • 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.
  • the impedance increasing means is preferably means for increasing the volume of the exhaust chamber.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • the plasma CVD film forming apparatus 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.
  • 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.
  • the plasma ignition means includes a high-voltage DC power source
  • the spark generation unit includes a spark electrode connected to the high-voltage DC power source, and a ground electrode.
  • high-voltage DC power is used as an energy source for generating sparks.
  • 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.
  • low-frequency power is used as an energy source for generating sparks.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • reaction chamber has a frequency of 100 kHz.
  • 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 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. .
  • the present invention 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.
  • 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. .
  • 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.
  • the plasma CVD film forming apparatus 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.
  • 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
  • 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.
  • the main axis of the container almost coincides with the main axis of the internal electrode.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • a volatile gas containing the constituent elements of the thin film is selected.
  • a publicly known volatile raw material gas is used as the raw material gas for forming the thin film having gas barrier properties.
  • 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.
  • 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.
  • 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.
  • the DLC film referred to in the present invention is an i-carbon film or a hydrogenated amorphous carbon film (a-C:
  • 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
  • a Si-containing hydrocarbon-based gas is used as a source gas for forming a Si-containing DLC film.
  • SiO film silicon oxide film
  • 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.
  • 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.
  • 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.
  • the frequency force ⁇ 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.
  • 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.
  • 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
  • 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
  • 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.
  • the capacitance of the internal space corresponding to the opening 32a is added to C. Spacer 36 is also in the clearance.
  • 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.
  • Z represents the plasm generated outside the plastic container 8, for example, in the exhaust chamber 5.
  • f is a low frequency
  • 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.
  • 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.
  • low frequency power of 400 kHz is output from the power supply 27.
  • the relationship C> C preferably the relationship C >> C holds.
  • 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 4 the result of Equation 4 is obtained from Equation 1 and Equation 2.
  • the difference (impedance B—impedance A) is f force, and when C-C is positive, that is, the relationship of C> C
  • 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.
  • 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.
  • a magnetic field can be used to adjust the fine generation region or the density distribution of the plasma.
  • 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.
  • 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.
  • a pointed portion 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).
  • 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.
  • Group 4A metal oxides Group 2B metal oxides such as ZnO, Group 3A metal oxides such as Y 2 O
  • 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.
  • MgO series MgO-AlO, MgO-TiO, MgO-ZrO, MgO-
  • a small amount of rare earth oxides such as NbO, LaO or SeO may be added to the layer material.
  • 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.
  • a method for producing a gas-nore plastic container 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.
  • 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,
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • low frequency power for example, 1 MHz
  • low frequency power for example, 1 MHz
  • 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.
  • 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.
  • 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.
  • the spacer 36 made of a dielectric is disposed, abnormal discharge does not occur.
  • 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.
  • 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.
  • the vacuum valve 12 is closed and the supply of the raw material gas is stopped.
  • 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.
  • the film formation time is as short as several seconds.
  • the DLC film is formed to a thickness of 0.003-5 ⁇ m.
  • 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.
  • the gas plastic plastic container manufacturing apparatus 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 space
  • Impedance increasing means is provided to increase dance B relative to impedance A as a reference.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • polytetrafluoroethylene tetrafluoroethylene “barfluoroalkyl bilayer copolymer”, tetrafluoroethylene “hexafluoropropylene copolymer”, polyphenylene oxide, polyimide, polyether. Sulphone, 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 4B. At this time, the space between the exhaust chamber 5 and the insulator spacer 4B is sealed by the O-ring 38.
  • 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.
  • 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.
  • 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.
  • 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.
  • the container according to the present invention is the same as in the case of Embodiment A.
  • 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.
  • a volatile gas containing the constituent elements of the thin film is selected.
  • a publicly known volatile raw material gas can be used as the raw material gas for forming the gas barrier thin film.
  • the source gas for example, when forming a DLC film, it is the same as in the case of Embodiment A.
  • the DLC film is the same as in the case of Embodiment A.
  • SiO film silicon oxide film
  • 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 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.
  • 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.
  • the gas barrier plastic container manufacturing apparatus has impedance increasing means based on the configuration described above.
  • the impedance increasing means has a plurality of modes.
  • 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 is provided in the gas barrier plastic container manufacturing apparatus 100B of the first mode (B).
  • 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 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.
  • 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).
  • 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.
  • LCR meter 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.
  • C is the LCR for insulator spacer 4B and exhaust chamber 5.
  • Z is the plasma generated in the reaction chamber 3B.
  • Z represents the impedance of the plasma generated in the reaction chamber 3B.
  • each side of Z and Z represents a sheath.
  • the impedance B of C is expressed by Equation 7. Where f is high frequency or low frequency
  • the frequency of the wave is the frequency of the wave.
  • the manufacturing apparatus 100B in Fig. 4 is designed so that the relationship of C> C is established.
  • 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
  • Equation 8 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.
  • Equation 9 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.
  • C> C preferably C >> C.
  • 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.
  • 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.
  • 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
  • the manufacturing apparatus 100B of Fig. 4 is configured such that the relationship C> C, preferably the relationship C>> C holds.
  • 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.
  • 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.
  • a high frequency power source 51 is connected to a reaction chamber 3B (external electrode) via an automatic matching unit 50.
  • 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).
  • the sub chamber 52 communicates with the exhaust chamber 5 through the opening 54 as an impedance increasing means.
  • a movable partition 53 is provided in the sub chamber 52. 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.
  • 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.
  • the volume of the sub chamber 52 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.
  • 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
  • C is an insulator spacer
  • 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
  • the volume of the internal space 31 can be increased by increasing it.
  • the impedance A of C is expressed by Equation 6.
  • the impedance B of C is the number 7
  • Equation 13 the capacitance C of a capacitor is expressed by Equation 13. ⁇ is the dielectric constant, S is the electrode area, and d is the distance between the electrodes.
  • Peedance B increases.
  • 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.
  • 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.
  • 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.
  • a high frequency power supply 51 is connected to a reaction chamber 3B (external electrode) via an automatic matching unit 50.
  • 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).
  • 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
  • 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.
  • 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.
  • 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.
  • Impedance B is given by Equation 7.
  • F is a high frequency and is constant. Therefore, impedance A is constant.
  • One dance B increases.
  • 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.
  • only the generation of plasma in the internal space 31 of the exhaust chamber 5 can be suppressed.
  • 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.
  • 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.
  • a high frequency power source 51 is connected to a reaction chamber 3B (external electrode) via an automatic matching unit 50.
  • 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).
  • variable capacitor 70 connected in series is provided between the connection of the exhaust chamber 5 and the ground as an impedance increasing means. .
  • FIG. 8 shows a bipolar discharge type circuit corresponding to the gas barrier plastic container manufacturing apparatus of the fourth embodiment (B).
  • C is a variable capacitor 7
  • a capacitance of 0 is shown.
  • C is the capacitance of insulator spacer 4B, C
  • each side of Z and Z represents a sheath.
  • impedance A of ⁇ is expressed by Equation 6.
  • f is a high frequency and is constant. Therefore, impedance A is constant.
  • Impedance B increases by reducing the capacitance C of variable capacitor 70.
  • impedance A is constant
  • impedance B can be relatively increased with impedance A as a reference.
  • 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.
  • the source gas supply pipe 9 is inserted into the plastic container 8.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the filter unit 25 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.
  • impedance B is based on impedance A.
  • 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.
  • the following secondary effects can be obtained by superimposing low-frequency power on high-frequency power.
  • the deposition rate is reduced compared to when only high-frequency power is supplied.
  • 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.
  • the film thickness distribution along the main axis direction of the container is made uniform.
  • 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.
  • ions can be accelerated by the high-frequency electric field (Vpp) with the superposition of 400 kHz.
  • Vpp high-frequency electric field
  • 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.
  • 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.
  • 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.
  • 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.
  • a manufacturing method according to the second embodiment (B) will be described with reference to FIG.
  • the volume of the exhaust chamber 5 is increased in order to increase the impedance B.
  • the difference from the manufacturing method according to the first embodiment (B) will be mainly described.
  • 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.
  • 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
  • the volume of the exhaust chamber 5 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
  • impedance A increases. Therefore, increase V to increase the volume of exhaust chamber 5.
  • the raw material gas in the plastic container 8 is turned into plasma using high frequency power as an energy source.
  • 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.
  • 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.
  • 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.
  • the generation of plasma in the exhaust path leading to the exhaust chamber 5 and then to the vacuum pump 23 is suppressed.
  • 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.
  • energy consumption is diverted to the generation of plasma in the internal space 30B of the reaction chamber 3B.
  • 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.
  • a manufacturing method according to the third embodiment (B) will be described with reference to FIG.
  • the insulator spacer 4B is changed to a thicker insulator spacer 4Ba.
  • the difference from the manufacturing method according to the first embodiment (B) will be mainly described.
  • 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).
  • the insulator spacer 4B is changed to a thicker insulator spacer 4Ba.
  • 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.
  • high-frequency power for example, 13.56 MHz
  • Insulator spacers 4Ba can be changed anytime before high-frequency power is supplied.
  • 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
  • impedance A increases. Therefore, by increasing the thickness of insulator spacer 4B, C
  • 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).
  • the gas barrier thin film is formed in a state where the impedance B is relatively increased with the impedance A as a reference. .
  • 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.
  • 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 (
  • 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 (
  • Impedance B is increased by reducing the capacitance (capacitance C of the capacitor).
  • the source gas is blown out into the plastic container 8 under a predetermined reduced pressure.
  • variable capacitor 70 is adjusted to be small.
  • 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
  • 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.
  • 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). .
  • the impedance B can be reduced by adjusting the capacitance C of the variable capacitor 70 to be small.
  • the gas barrier thin film is formed in a relatively high state with respect to the flow rate A.
  • 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.
  • the film formation time is as short as several seconds.
  • the DLC film is formed to a thickness of 0.003 to 5 xm.
  • 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.
  • the plasma CVD film forming apparatus 100C of the first embodiment (C) 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
  • the plasma ignition means having the spark generator 40 is a DC discharge system using a high-voltage DC power supply 290.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the container according to the present invention is the same as in the case of Embodiment A.
  • the resin used in molding the plastic container 8 of the present invention is the same as that in the embodiment A.
  • 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.
  • 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.
  • 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.
  • a volatile gas containing the constituent elements of the thin film is selected.
  • a publicly known volatile raw material gas can be used as the raw material gas for forming the gas barrier thin film.
  • the source gas for example, when forming a DLC film, it is the same as in the case of Embodiment A.
  • the DLC film is the same as in the case of Embodiment A.
  • SiO film silicon oxide film
  • a mixed gas of silane and oxygen Alternatively, a mixed gas of HMDSO and oxygen is used as the source gas.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • C 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.
  • Z represents the impedance of the plasma generated in the reaction chamber 3C, and Z is pi p2 in the exhaust chamber 5.
  • the impedance A of C is given by Equation 15.
  • the impedance B of C is given by Equation 15.
  • the film deposition system 100C in Fig. 10 is designed so that the relationship C> C is established.
  • 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
  • impedance B 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.
  • the relationship C> C preferably the relationship C>> C holds.
  • 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.
  • the plasma CVD film forming apparatus 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.
  • the plasma ignition means has a high-voltage DC power supply 290
  • 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.
  • 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.
  • the conductor 41 is a spark electrode
  • the source gas supply pipe 9 is a ground electrode.
  • the ground electrode serves as the counter electrode
  • 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.
  • FIG. 13 shows a diagram for explaining the details of FIG.
  • FIG. 13 (a) is a BB cross-sectional view
  • FIG. 13 (b) is a partially enlarged schematic view of the spark generating portion 40.
  • 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.
  • 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.
  • FIG. 14 an AA cross-sectional view and a partially enlarged schematic view of the spark generating portion 40 are as shown in FIG.
  • 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.
  • the spark electrode and the ground electrode are separated by 2-5 mm, for example.
  • 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.
  • FIG. 15 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.
  • a BB cross-sectional view and a partial enlarged schematic view of the spark generating portion 40 are as shown in FIG.
  • low-frequency power is supplied to the spark generating unit 40 in the same manner as the film forming apparatus 300C shown in FIG.
  • 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.
  • the insulator 42 is preferably an insulator.
  • 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.
  • the source gas supply pipe 9 is inserted into the plastic container 8.
  • 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.
  • 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.
  • 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.
  • 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.
  • a DLC film is formed on the inner surface of the plastic container 8.
  • 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.
  • 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.
  • Switch 280 is turned on almost simultaneously with the supply of low-frequency power.
  • 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.
  • sparks are generated between the source gas supply pipe 9 and the DC gas discharge.
  • the relationship C> C preferably the relationship C>> C,
  • 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.
  • 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.
  • the vacuum valve 12 is closed and the supply of the raw material gas is stopped.
  • the vacuum pump 23 exhausts the air.
  • the vacuum valve 22 is closed and the exhaust is finished.
  • the pressure in the vacuum chamber 7C is 6.6 to 665 Pa.
  • the vacuum valve 18 is opened. Thereby, the vacuum chamber 7C is opened to the atmosphere.
  • the film formation time is as short as several seconds.
  • the DLC film is formed to a thickness of 0.003 to 5 ⁇ m.
  • the switch 280 is turned on at the same time as the supply of the low frequency power.
  • 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.
  • ignition failure is reduced and ignition sustainability is imparted.
  • detection means such as an ignition monitor. The spark may be stopped immediately after the plasma is ignited.
  • the switch 280 is turned on at the same time as the supply of the low frequency power.
  • 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.
  • 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.
  • the switch 280 is turned on at the same time as the supply of the low-frequency power.
  • 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.
  • 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.
  • 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.
  • 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.
  • Film uniformity (%) (Average film thickness A—Average film thickness B) / (Average film thickness A + Average film thickness B) X 100
  • 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)
  • 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.
  • 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 More than 0.2 mg 0.4 mg or less: ( ⁇ ) Foreign matter adhering slightly, but no problem in continuous operation for a long time.
  • 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.
  • the oxygen permeability 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 0.015ml Z day Over Z container (X) There is a problem as an oxygen barrier container.
  • 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.
  • 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.
  • the combined capacitance of the PET bottle 8 and the inner space 30 of the outer electrode 3 is C
  • the combined capacitance of the insulating member 4 and the inner space 31 of the exhaust chamber 5 is C.
  • C> C the relationship was established. Generation of foreign matter
  • 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.
  • 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.
  • a high-frequency power supply frequency 13.56 MHz
  • the results are shown in Table 1.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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)
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • variable capacitor 70 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a discharge sensor photo diode, Connected to a Yamatake photoelectric sensor, HPX-MA-063
  • 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.
  • 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)
  • 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.
  • 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
  • (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.
  • test 2 that supplied high-frequency power was compared with test 1 that supplied low-frequency power
  • 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.
  • 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.
  • (Trial 3) shows that film formation at the container mouth was suppressed. This is probably because the central part of the plasma generation has shifted downward.
  • 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.
  • the number of times of film formation was 30,00 0 times, the plasma non-ignition trouble was 0 times.
  • 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.
  • the film formation was repeated under the conditions of Test 1 without operating the plasma ignition means.
  • Test 1 the conditions of Test 1 without operating the plasma ignition means.
  • 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.
  • 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.

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Abstract

L'invention concerne un dispositif de production de contenants de plastique imperméables aux gaz, permettant d'augmenter la productivité par une réduction des opérations d'élimination périodique de matières étrangères dans une chambre d'évacuation et le passage d'évacuation la prolongeant, et ddes opérations de remplacement de l'électrode externe pour modifier le profil du contenant. Dans un dispositif permettant de former une couche mince présentant des caractéristiques de barrière aux gaz, sur la surface de la paroi interne d'un contenant de plastique au moyen d'un procédé de dépôt chimique en phase vapeur (CVD), on place un séparateur diélectrique dans l'espace formé entre la surface de la paroi interne d'une électrode externe incidente, et la surface de la paroi externe du contenant de plastique. Si l'on considère que C1 représente la capacité combinée du contenant de plastique lui-même et de son espace interne, et que C2 représente la capacité combinée de l'espace extérieur au contenant de plastique, à l'extérieur de l'espace interne d'une unité de dépôt de couche comprenant l'espace interne d'une chambre sous vide et de l'espace interne de la chambre d'évacuation, la relation suivante est respectée : C1>C2. On fournit à l'électrode externe une énergie basse fréquence de 400kHz-4MHz.
PCT/JP2007/058458 2006-09-29 2007-04-18 Dispositif de production d'un contenant de plastique imperméable aux gaz et procédé de production correspondant WO2008041386A1 (fr)

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US8883257B2 (en) 2009-04-13 2014-11-11 Kirin Beer Kabushiki Kaisha Method for manufacturing gas barrier thin film-coated plastic container
US9953809B2 (en) 2015-09-02 2018-04-24 Industrial Technology Research Institute Apparatus for coating a film in a container and method for coating the film

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JP6949426B2 (ja) * 2017-09-27 2021-10-13 株式会社吉野工業所 バリア膜形成装置及びバリア膜形成方法

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JP2005194606A (ja) * 2004-01-09 2005-07-21 Mitsubishi Heavy Ind Ltd プラスチック容器内面へのバリヤ膜形成装置および内面バリヤ膜被覆プラスチック容器の製造方法
JP2005281844A (ja) * 2004-03-31 2005-10-13 Mitsubishi Heavy Ind Ltd 成膜装置及び方法
JP2007113052A (ja) * 2005-10-19 2007-05-10 Mitsubishi Shoji Plast Kk 反応室外でのプラズマ発生の抑制方法並びにガスバリア性プラスチック容器の製造方法及びその製造装置
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JPH10147878A (ja) * 1996-11-19 1998-06-02 Kokusai Electric Co Ltd プラズマｃｖｄ装置
JP2005113202A (ja) * 2003-10-08 2005-04-28 Mitsubishi Shoji Plast Kk プラズマｃｖｄ成膜装置
JP2005194606A (ja) * 2004-01-09 2005-07-21 Mitsubishi Heavy Ind Ltd プラスチック容器内面へのバリヤ膜形成装置および内面バリヤ膜被覆プラスチック容器の製造方法
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Publication number Priority date Publication date Assignee Title
US8883257B2 (en) 2009-04-13 2014-11-11 Kirin Beer Kabushiki Kaisha Method for manufacturing gas barrier thin film-coated plastic container
US9953809B2 (en) 2015-09-02 2018-04-24 Industrial Technology Research Institute Apparatus for coating a film in a container and method for coating the film

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