WO2010119578A1 - ガスバリア性薄膜コーティングプラスチック容器の製造方法 - Google Patents
ガスバリア性薄膜コーティングプラスチック容器の製造方法 Download PDFInfo
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- WO2010119578A1 WO2010119578A1 PCT/JP2009/061582 JP2009061582W WO2010119578A1 WO 2010119578 A1 WO2010119578 A1 WO 2010119578A1 JP 2009061582 W JP2009061582 W JP 2009061582W WO 2010119578 A1 WO2010119578 A1 WO 2010119578A1
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- plastic container
- external electrode
- film
- gas
- thin film
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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
- C23C16/44—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
- B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D23/00—Details of bottles or jars not otherwise provided for
- B65D23/02—Linings or internal coatings
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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
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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
- C23C16/22—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
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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
- C23C16/22—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
- C23C16/27—Diamond only
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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
- C23C16/44—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32532—Electrodes
- H01J37/32541—Shape
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32532—Electrodes
- H01J37/32568—Relative arrangement or disposition of electrodes; moving means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/332—Coating
Definitions
- the present invention relates to a method for producing a gas barrier thin film coated plastic container in which a thin film having a gas barrier property is formed on the inner wall surface of a plastic container by a plasma CVD (chemical vapor deposition) method.
- the container is filled with, for example, a beverage / food, but the storage performance of the beverage / food is improved.
- Plastic containers are easy to absorb odors and have poor gas barrier properties compared to coffee bottles and cans, so it was difficult to use them for oxygen-sensitive beverages such as beer and sparkling liquor. Therefore, a method and apparatus for coating a hard carbon film (diamond-like carbon (DLC)) or the like has been disclosed in order to solve the problems of sorption and gas barrier properties in plastic containers. For example, by using an external electrode having an internal space substantially similar to the outer shape of the target container and an internal electrode inserted into the container through the mouth of the container and also serving as a source gas introduction pipe, Discloses an apparatus for coating a hard carbon film (see, for example, Patent Document 1 or 2).
- DLC diamond-like carbon
- high-frequency power is applied to the external electrode in a state where a carbon source gas such as aliphatic hydrocarbons or aromatic hydrocarbon carbon is supplied as a source gas in the container.
- a carbon source gas such as aliphatic hydrocarbons or aromatic hydrocarbon carbon
- the source gas is turned into plasma between both electrodes, and the ions in the generated plasma are attracted by 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. Is formed.
- a power source for generating plasma a power source having an industrial frequency of 13.56 MHz which is easy to use and obtain is used in a conventional mass production apparatus.
- the inner wall surface of the external electrode and the outer wall surface of the plastic container A technique is disclosed in which a spacer made of a dielectric material is arranged in a gap space between the electrodes, the combined electrostatic capacity of the device is adjusted, and low frequency power having a frequency of 400 kHz to 4 MHz is supplied to an external electrode (for example, In addition, use a vacuum chamber in which the upper part of the external electrode is replaced with a dielectric, adjust the combined capacitance of the device, and apply low frequency power with a frequency of 400 kHz to 4 MHz to the external electrode.
- a technique for supplying is disclosed (for example, see Patent Document 4).
- the sheath length of the discharge plasma and the radius of the mouth of the container are maintained in a predetermined relationship, and a low frequency power source of 0.1 to 5 MHz is used.
- the technique to do is disclosed (for example, refer to Patent Document 5).
- Japanese Patent No. 2788412 Japanese Patent No. 3072269 JP 2008-088471 A JP 2008-088472 A JP 2005-281844 A
- the performance of the container mainly requires gas barrier properties, coloration of the film, and adhesion of the film, and in terms of production efficiency, the short process time and operation stability are mainly required. Desired.
- the frequency of the power source for plasma generation is as high as 13.56 MHz, which is generally used, accumulation of foreign matters such as carbon powder in the exhaust system is promoted as described in Patent Documents 3 and 4. In order to suppress this, a power source having a frequency lower than 13.56 MHz is used.
- an object of the present invention is to suppress the accumulation of foreign substances such as carbon powder without using a specially shaped external electrode, and to reduce gas barrier properties and film coloration (difference in the color concentration of the film depending on the part of the container). It is to produce a plastic container coated with a thin film with good film adhesion (that is, performance viewed from the viewpoint that color unevenness is small) and color density is low.
- the foreign matter deposited in the exhaust chamber or the like is carbon powder or carbon dust (also simply referred to as dust).
- the present inventors have set the frequency of the power source for plasma generation within the range of 5.5 to 6.5 MHz, so that the accumulation of foreign matters can be specifically performed.
- the present invention has been completed by finding that a thin film can be coated with less gas barrier properties, film coloration and film adhesion. That is, in the method for producing a gas barrier thin film-coated plastic container according to the present invention, the step of housing the plastic container in the external electrode serving as the film forming unit and the internal electrode serving as the source gas supply pipe are disposed inside the plastic container.
- the plastic container is accommodated in a state in which the mouth of the container faces downward in the process of accommodating the plastic container in the external electrode. Foreign matter mixed in the internal space of the container before film formation is easily removed, and as a result, the occurrence of film formation defects in the film is prevented. Furthermore, the reattachment of the thin film source gas-derived substance to the bottle is prevented at the end of film formation.
- the height of the container is h, and the bottom of the container is a reference point.
- the source gas supply pipe is inserted from the mouth of the container so that the tip of the source gas supply pipe is at a position in the range of 1/2 ⁇ h to 2/3 ⁇ h. preferable.
- the method for producing a gas barrier thin film-coated plastic container according to the present invention includes a form in which an external electrode whose inner space has a bottomed cylindrical shape is used.
- the method for producing a gas barrier thin film-coated plastic container according to the present invention includes a form in which a carbon film, a silicon-containing carbon film, or a metal oxide film is formed as the gas barrier thin film.
- the plastic container includes a form having a capacity of 500 ml or more.
- the method for producing a gas barrier thin film coated plastic container according to the present invention includes a form in which the plastic container is a polyethylene terephthalate container.
- the present invention manufactures a plastic container coated with a thin film that suppresses the accumulation of foreign matters such as carbon powder and has good gas barrier properties, film coloration, and film adhesion without using a specially shaped external electrode. can do.
- External electrodes provided with an internal space (hereinafter referred to as an internal space) having an inner surface shape that is substantially the same as or similar to the outer surface shape of the container, except for the plasma generation power source, as a film forming apparatus to be used
- an internal space having an inner surface shape that is substantially the same as or similar to the outer surface shape of the container, except for the plasma generation power source
- a film forming apparatus having the same type as a film forming apparatus having a so-called similar external electrode for example, a film forming apparatus disclosed in Patent Document 1 or 2 or the like) can be used.
- a film forming apparatus having a so-called cylindrical external electrode in which the shape of the internal space provided in the external electrode is a bottomed cylindrical shape other than the power source for generating plasma for example, Patent Document 3 or 4
- a film forming apparatus having a cylindrical external electrode a gap is formed between the outer surface of the shoulder portion of the container and the inner surface of the internal space of the external electrode.
- a spacer such as a dielectric is inserted in the gap. It may or may not be included.
- an electrode having an inner space larger than that of the bottle can be used.
- a spacer such as a dielectric may be inserted in the gap between the periphery of the bottle and the inner surface of the inner space of the outer electrode, or You don't have to put it in.
- a film forming apparatus to be used except for the plasma generating power source, a film forming apparatus (the gap between the outer surface of the shoulder portion of the container and the inner surface of the internal space of the external electrode is set to have a predetermined relationship (for example, a film forming apparatus of the same type as in Patent Document 6) can be used.
- Japanese Patent No. 4188315 Japanese Patent No. 4188315
- FIG. 1 is a schematic view of a film forming apparatus having a similar external electrode.
- FIG. 1 is a longitudinal sectional view, and this manufacturing apparatus has a rotationally symmetric shape around the main axis of the plastic container 8.
- the main axis of the container substantially coincides with the main axis of the internal electrode.
- the film forming apparatus 100 includes an external electrode 3 serving as a film forming unit that accommodates the plastic container 8, an internal electrode 9 serving as a source gas supply pipe that is detachably disposed inside the plastic container 8, and the external electrode 3.
- An insulating member 4 that electrically insulates the external electrode 3 from the exhaust chamber 5 is provided.
- the external electrode 3 is formed in a hollow with a conductive material such as metal to form a film forming unit (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.
- the external electrode 3 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 an O-ring 10.
- the plastic container 8 can be mounted by detaching the lower external electrode 1 from the upper external electrode 2.
- the external electrode 3 is sealed from the outside by an O-ring 37 disposed between the insulating member 4 and the external electrode 3 and an O-ring 10 disposed between the upper external electrode 2 and the lower external 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 an O-ring. You may do it.
- the plastic container 8 generally has a shape in which the diameter of the mouth part is reduced with respect to the body part, 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 inner space 30 formed in the external electrode 3 has an inner surface shape substantially the same as the outer surface shape of the plastic container 8, and when the plastic container 8 is accommodated in the inner space 30, there is almost no gap. However, a gap of about several centimeters may be allowed. The gap is preferably filled with a derivative spacer.
- the insulating member 4 has an opening 32 a 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 exhaust chamber 5 is formed hollow with a conductive material such as metal and has an internal space 31.
- the exhaust chamber 5 and the insulating member 4 are sealed with an O-ring 38. Then, in order to make the internal space 31 and the internal space 30 communicate with each other in air, an opening 32b having substantially the same shape is provided in the lower portion of the exhaust chamber 5 corresponding to the opening 32a.
- the exhaust chamber 5 is connected to a vacuum pump 23 via 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 lid 6 is formed, the external electrode 3 is sealed, and the film forming unit 7 that can be sealed is assembled.
- the plastic container according to the present invention is, for example, a plastic bottle, cup or tray. It includes a container that is used in the open state without using a lid, a stopper, a seal, or a container. The size of the opening is determined according to the contents.
- the plastic container 8 has a predetermined thickness having moderate rigidity and does not include a soft packaging material formed of a sheet material having no rigidity.
- the filling material 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.
- Resin used when molding the plastic container 8 is, for example, polyethylene terephthalate resin (PET), polyethylene terephthalate-based copolyester resin (copolymer using cyclohexane dimethanol instead of ethylene glycol as the alcohol component of polyester is PETG) Called Eastman Chemical), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin (PP), cycloolefin copolymer resin (COC, cyclic olefin copolymer), ionomer resin, poly-4-methyl Pentene-1 resin, polymethyl methacrylate resin, polystyrene resin, ethylene-vinyl alcohol copolymer resin, acrylonitrile resin, polyvinyl chloride resin, polyvinyl chloride Styrene resins - Den resins, polyamide resins, polyamide-imide resins, polyacetal resins, polycarbonate resins, polysulfone resins, te
- 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.
- a gas outlet 9a that is, an opening of a gas flow path is provided.
- 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 disposed in the external electrode 3 and disposed inside the plastic container 8 from the mouth. That is, the internal electrode 9 is inserted into the internal space 30 of the external electrode 3 through the internal space 31 and the openings 32a and 32b with the upper part of the inner wall of the exhaust chamber 5 as the base end.
- the internal electrode 9 is preferably grounded.
- the tip (9a) of the internal electrode 9 is disposed inside the plastic container 8. The detailed position of the tip (9a) of the internal electrode 9 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 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.
- the source gas generation source 15 generates a hydrocarbon gas source gas such as acetylene.
- the thin film having gas barrier properties 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 metal oxide film such as a SiOx film.
- a volatile gas containing the constituent elements of the thin film is selected.
- a publicly known volatile raw material gas is used as a raw material gas when forming a thin film having gas barrier properties.
- gaseous or liquid aliphatic hydrocarbons for example, when forming a DLC film, gaseous or liquid aliphatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons, etc. at room temperature are used.
- 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 from the viewpoint of hygiene Is preferred.
- These raw materials may be used alone, or may be used as a mixed gas of two or more. Further, these gases may be diluted with a rare gas such as argon or helium.
- a silicon-containing DLC film is formed, a Si-containing hydrocarbon gas is used.
- Si-containing unit cost hydrogen gas and oxygen are supplied to a gas introduction pipe. The same applies to other metal oxide films, and a source gas containing the metal and oxygen are used.
- the DLC film referred to in the present invention is a film called i-carbon film or hydrogenated amorphous carbon film (aC: H), and includes a hard carbon film.
- the DLC film is an amorphous carbon film and also has SP 3 bonds.
- a hydrocarbon gas such as acetylene gas is used as a source gas for forming the DLC film
- a Si-containing hydrocarbon gas is used as a source gas for forming the Si-containing DLC film.
- a Si-containing hydrocarbon gas is used.
- silicified hydrocarbon gas or silicic acid gas include silicon tetrachloride, silane (SiH 4 ), hexamethyldisilane, vinyltrimethylsilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, and methyltriethoxysilane.
- AlOx film aluminum oxide thin film
- trialkylaluminum, trimethylaluminum, and triethylaluminum are dialkylaluminum, triisopropylaluminum, tri-n-butylaluminum, dimethylisopropylaluminum. Is used.
- 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.
- 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 plasma generation power supply means 35 includes a plasma generation power source 27 and an automatic matching unit 26 connected to the plasma generation power source 27, and the plasma generation power source 27 is connected to the external electrode 3 via the automatic matching unit 26. Connected. When the output of the plasma generating power supply 27 is applied to the external electrode 3 and a potential difference is generated between the internal electrode 9 and the external electrode 3, the raw material gas supplied into the plastic container 8 is turned into plasma.
- the frequency of the plasma generating power supply 27 is in the range of 5.5 to 6.5 MHz. In this range, a fixed frequency power supply is used. Further, a frequency variable power source may be used in this range.
- the film forming unit 7 is formed so that the mouth of the plastic container 8 faces upward, but the film forming unit 7 may be formed so that the mouth of the plastic container 8 faces downward. Foreign matter mixed in the internal space of the container before film formation is easily removed, and as a result, the occurrence of film formation defects in the film is prevented. Furthermore, the reattachment of the thin film source gas-derived substance to the bottle is prevented at the end of film formation.
- the manufacturing method of the gas barrier thin film coated plastic container according to the present embodiment includes (1) a step of accommodating the plastic container 8 in the external electrode 3 serving as the film forming unit 7, and (2) a raw material gas supply pipe inside the plastic container 8. A step of disposing the internal electrode 9 to become, (3) a step of evacuating the gas inside the external electrode 3 by operating the vacuum pump 23, and (4) blowing the raw material gas into the plastic container 8 under reduced pressure.
- the power source frequency of the plasma generating power source 27 that supplies power to the external electrode 3 is set to 5.5 to 6.5 MHz, the source gas is turned into plasma, and a gas barrier is formed on the inner wall surface of the plastic container 8. A step of forming a thin film having properties.
- 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. It exhausts via the insulated exhaust chamber 5. 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. At this time, the pressure in the film forming unit 7 is, for example, 0.1 to 50 Pa.
- the automatic matching unit 26 matches the impedance by the inductance L and the capacitance C so that the reflected wave from the entire electrode supplying the output is minimized.
- the locations of the “shoulder” and “body” of the plastic container 8 are shown.
- the “shoulder” is the lower part of the neck that is reduced in diameter along the upper part of the container main shaft, and the “torso” is the center height of the small torso below the shoulder. It was a place.
- the power supply frequency By setting the power supply frequency to a narrow frequency range of 5.5 to 6.5 MHz, specifically, (1) the gas barrier property is maximized, and (2) the color derived from carbon contained in the DLC film is increased. High quality of the container that is thin and has less color unevenness between the shoulder part and the body part, so that the design of the container is high, and (3) there is little adhesion of dust from the source gas in the exhaust chamber 5 And increased production efficiency (less frequent cleaning of equipment). If the power supply frequency is out of the frequency range of 5.5 to 6.5 MHz, the advantages (1) to (3) cannot be obtained at the same time.
- the color derived from the carbon in the DLC film appears darker than the shoulder side on the trunk side, and the average color appears. The color is also dark. This tendency becomes remarkable when the bottle size is 500 ml or more.
- the adhesion of the film decreases.
- the power supply frequency exceeds 6.5 MHz
- the coloration derived from carbon in the DLC film appears darker than the body side on the shoulder side, and when the frequency reaches 13.56 MHz, the average coloration is also apparent. It ’s dark.
- the adhesion of the dust derived from the source gas in the exhaust chamber 5 increases. Further, the vicinity of the opening 32b of the exhaust chamber 5 is etched by plasma, and the surface of the exhaust chamber 5 is shaved.
- the power supply frequency When the power supply frequency is shifted to the high frequency side, the position of the center of the plasma (the part with the highest concentration) moves to the mouth side of the container.
- a power supply frequency of 5.5 to 6.5 MHz it is considered that the plasma distribution satisfies all of the gas barrier properties, coloration properties, and minimization of dust accumulation in the exhaust chamber.
- the power output (W) without depending on the capacity of the container, for example, the capacity of 250 ml to 2 liters, For example, it does not depend on the output of 400 to 2000 W).
- a suitable power supply frequency that can simultaneously obtain the merits (1) to (3) is substantially affected by the width and length of the shape if the film forming unit 7 has a substantially bottomed cylindrical shape. It is thought that there is nothing. Therefore, by setting the power supply frequency to 5.5 to 6.5 MHz, a conventional type film forming apparatus can be used without adding a complicated structure to the manufacturing apparatus or adding another structure. If the power supply frequency is 5.5 to 6.5 MHz, the quality can be maximized and the production efficiency can be improved.
- the tip (9a) of the internal electrode 9 is disposed inside the plastic container 8.
- the tip of the internal electrode (raw material gas supply pipe) 9 is 1/2 ⁇ h or more 2 as shown in FIG. It is preferably inserted so as to be in a position within a range of / 3 ⁇ h or less. If the tip of the internal electrode (source gas supply pipe) 9 is less than 1 / 2h, a film is likely to be attached to the bottom of the container and the lower part of the body more than necessary, and coloration may be conspicuous. Accumulation of carbon dust on the outer surface of the tube becomes significant. On the other hand, if it is at a position exceeding 2/3 ⁇ h, plasma ignition may be poor.
- the output of the plasma generating power supply 27 is stopped, the plasma is extinguished, and the DLC film formation is completed.
- the vacuum valve 12 is closed to stop the supply of the raw material gas.
- the vacuum pump 23 exhausts the hydrocarbon gas remaining in the film forming unit 7 and the plastic container 8. Thereafter, the vacuum valve 22 is closed, and the exhaust is finished.
- the pressure in the film forming unit 7 at this time is 1 to 100 Pa.
- the vacuum valve 18 is opened. Thereby, the film forming unit 7 is opened to the atmosphere.
- the DLC film is formed to have a thickness of 5 to 100 nm.
- a DLC film was formed on the inner surface of a 500 ml PET bottle (resin amount 29 g, height 204 mm) and a 280 ml PET bottle (resin amount 26 g, height 132 mm).
- the source gas was acetylene, the gas flow rate was 80 sccm (500 ml PET bottle), 90 sccm (280 ml PET bottle), and the film formation time was 2 seconds.
- a power source for generating plasma a frequency variable power source in the range of 2.50 to 13.56 MHz (2.5 MHz to 7 MHz: Noda RF Technologies, model number NR1.5F5-7M-01) (13.56 MHz: Japan Radio) Model No. NAH-1013-2Y) was used. Film formation was performed at various frequencies in the range of 2.50 MHz to 13.56 MHz. In all samples, the film thickness of the DLC film was approximately 20 nm.
- Table 1 shows oxygen barrier properties when a DLC film is formed on a 500 ml PET bottle.
- the oxygen permeability of this container was measured under the conditions of 23 ° C. and 90% RH using an Otran 2/20 manufactured by Modern Control, and measured values 72 hours after the start of nitrogen gas replacement (OTR in Table 1). Value).
- the film thickness of the DLC film was measured using Alpha-step iQ manufactured by KLA tencor, and Table 2 shows the oxygen barrier properties when the DLC film was formed on a 280 ml PET bottle.
- the BIF value is a value indicating how many times the oxygen barrier property is improved with reference to the uncoated bottle.
- the results of Tables 1 and 2 are plotted in FIG.
- the color of the plastic container was evaluated using the coloring degree b * value as an index.
- the b * value is the color difference of JISK 7105-1981, and is obtained from the tristimulus values X, Y, and Z according to Equation 1.
- a Hitachi U-3500 self-recording spectrophotometer equipped with a 60 ⁇ integrating sphere accessory device (for infrared, visible and near infrared) was used.
- an ultrasensitive photomultiplier tube R928: for ultraviolet and visible
- a cooled PbS for near infrared region
- the b * value of this example is the same as that calculated in the form including the absorptivity of the PET container. Show.
- the b * and visual correlation in the present invention is roughly as shown in Table 3.
- the b * value of the untreated PET container is in the range of 0.6 to 1.0. Moreover, it can be said that a b * value of 2 or less is colorless and transparent.
- Table 4 shows the results of evaluating the color developability when a DLC film was formed on a 500 ml PET bottle.
- Table 5 shows the results of evaluating the color developability when a DLC film was formed on a 280 ml PET bottle. The results of Table 4 are plotted in FIG. The results of Table 5 are plotted in FIG.
- the “variation” of the 500 ml PET bottle was as follows.
- the “average” of the 500 ml PET bottle is the average coloring degree, and is as follows.
- the “variation” of 280 ml PET bottles was as follows.
- the “average” of 280 ml PET bottles is the average coloring degree, and is as follows.
- Table 6 shows the results of evaluating the adhesion when a DLC film is formed on a 500 ml PET bottle. Evaluation is carried out by maintaining a sodium hydroxide aqueous solution (0.01% by mass) at pH 9 at 65 ° C., immersing the container, before immersion (0 day), 1 day immersion (1 day), 2 day immersion (2 Day) The film was peeled when immersed for 3 days (3rd day) and for 4 days (4th day).
- ⁇ No peeling
- ⁇ There is a peeling piece less than 5 mm in length
- ⁇ There is a peeling piece of 5 mm or more in length
- Table 7 shows the results of evaluating the adhesion when a DLC film was formed on a 280 ml PET bottle. Evaluation is carried out by maintaining a sodium hydroxide aqueous solution (0.01% by mass) at pH 9 at 80 ° C., immersing the container, before immersion (0 day), 1 day immersion (1 day), 2 day immersion (2 Day) The film was peeled when immersed for 3 days (3rd day) and for 4 days (4th day).
- ⁇ No peeling
- ⁇ There is a peeling piece less than 5 mm in length
- ⁇ There is a peeling piece of 5 mm or more in length
- Table 8 evaluated the deposition of carbon dust when a DLC film was formed on a 500 ml PET bottle. A silicon wafer was placed on the outer surface of the source gas introduction pipe, which is substantially in the center of the exhaust chamber, and film formation was performed 10 times. The amount of dust deposited (nm) in F in the exhaust chamber was determined in FIG. The larger the deposition amount, the shorter the cleaning interval of the film forming apparatus. FIG. 6 shows the relationship between the power supply frequency and the amount of carbon dust deposited.
- Table 9 shows the change in mass of the source gas introduction tube when a DLC film was formed on a 500 ml PET bottle.
- a removable stainless steel cylindrical member is installed on the outer surface of the raw material gas introduction pipe located immediately downstream of the bottle, film formation is performed 100 times, and the mass change of the member at the location E in FIG. Evaluated.
- the larger the mass increase the greater the amount of dust accumulation.
- Considering error factors at the time of desorption it is considered that there is no significant difference between 2.5 MHz and 7 MHz.
- the mass was significantly reduced. This is probably because the center of the plasma was present near the mouth of the bottle, and the member was etched.
- FIG. 7 shows the relationship between the power frequency when a DLC film is formed on a 500 ml PET bottle and the change in mass of the member installed near the bottle mouth.
- Table 10 shows the mass change of the source gas introduction pipe when the DLC film was formed on the 280 ml PET bottle.
- a removable cylindrical member made of stainless steel is installed on the outer surface of the raw material gas introduction pipe located immediately downstream of the bottle, film formation is performed 100 times, and the mass change of the member at the location E in FIG. Evaluated. The larger the mass increase, the greater the amount of dust accumulation. Considering error factors at the time of desorption, it is considered that there is no significant difference between 2.5 MHz and 7 MHz. On the other hand, the mass decreased significantly at 13.56 MHz, which is considered to be because the center of the plasma was present near the mouth of the bottle and the member was etched.
- FIG. 8 shows the relationship between the power supply frequency when a DLC film is formed on a 280 ml PET bottle and the change in mass of the member installed near the bottle mouth.
- Table 11 shows the received light intensity of the optical sensor installed at the position D in FIG. 1 when a DLC film was formed on a 500 ml PET bottle.
- D is a viewing window on the outer surface of the exhaust chamber 10 cm away from the center of the gas introduction pipe.
- the received light intensity is related to the emission intensity of the plasma. The higher the received light intensity, the closer the plasma is to the exhaust chamber or the plasma is generated in the exhaust chamber. As a result, the higher the received light intensity, the wider the plasma distribution range in the exhaust chamber and the higher the plasma concentration, which means that the total dust accumulation amount in the exhaust chamber is large.
- Table 12 shows the received light intensity of the photosensor installed at the position D in FIG. 1 when a DLC film was formed on a 280 ml PET bottle. Further, FIG. 8 shows the relationship between the power supply frequency and the emission intensity in the exhaust chamber.
- FIG. 8 shows that the emission intensity increases as the power frequency increases. That is, it can be seen that the plasma moves upward along the container main axis direction. From FIG. 7, it can be seen that when the power source frequency is 13.56 MHz, the vicinity of the bottle mouth is etched, which is consistent with the result of FIG. According to the results of FIG. 6, the amount of dust accumulated in the exhaust chamber tends to increase as the power frequency increases.
- FIG. 3 it can be seen that the oxygen barrier property does not change with a tendency even when the power supply frequency is increased, and that it is specifically high at 5.5 to 6.5 MHz. It can be seen that even if the capacity of the container is different, it is specifically high at 5.5 to 6.5 MHz. Furthermore, according to FIG. 4, the variation of * b value is reduced from 5.5 to 6.5 MHz, and the average value of * b value is minimized, and the coloration property of the container is particularly good. It turns out that it becomes.
- FIG. 5 also has the same tendency, and it can be seen that the coloration property of the container is particularly good at 5.5 to 6.5 MHz even if the capacity of the container is different.
- the adhesiveness is improved by setting the electrode frequency to 5.5 MHz or more. Further, when the frequency is lower than 5.5 MHz, it can be seen from Tables 6 and 7 that the adhesion strength of the film decreases. This is thought to be a result of significant damage to the PET polymer chain due to increased ion bombardment on the inner surface of the PET bottle as the frequency decreases. On the other hand, when the frequency exceeds 6.5 MHz, the center position of the plasma is significantly biased toward the mouth side of the bottle, resulting in a decrease in the barrier property from the optimum level and variations in coloration.
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Abstract
Description
成膜ユニット7内は、真空バルブ18を開いて大気開放されており、外部電極3の下部外部電極1が上部外部電極2から取り外された状態となっている。次に上部外部電極2の下側から上部外部電極2内の空間にプラスチック容器8を差し込み、外部電極3の内部空間30内に設置する。この際、内部電極9はプラスチック容器8内に挿入された状態になる。次に、下部外部電極1を上部外部電極2の下部に装着し、外部電極3はO-リング10によって密閉される。以上の操作により、外部電極3の内部空間30にプラスチック容器8が収容され、かつ、プラスチック容器8の内部に内部電極9が配置される。
次に、プラスチック容器8の内部を原料ガスに置き換えするとともに所定の成膜圧力に調整する。すなわち、図1に示すように、真空バルブ18を閉じた後、真空バルブ22を開き、真空ポンプ23を作動させ、外部電極3の内部のガスを、絶縁部材4によって外部電極3と電気的に絶縁されている排気室5を経由して排気する。これにより、プラスチック容器8内を含む成膜ユニット7内が配管21を通して排気され、成膜ユニット7内が真空となる。このときの成膜ユニット7内の圧力は、例えば0.1~50Paである。
次に、真空バルブ12を開き、原料ガス発生源15においてアセチレンガス等の炭化水素ガスを発生させ、この炭化水素ガスを配管14内に導入し、マスフローコントローラー13によって流量制御された炭化水素ガスを配管11及びアース電位の内部電極(原料ガス供給管)9を通してガス吹き出し口9aから吹き出させる。これにより、炭化水素ガスがプラスチック容器8内に導入される。そして、成膜ユニット7内とプラスチック容器8内は、制御されたガス流量と排気能力のバランスによって、DLC膜の成膜に適した圧力(例えば1~100Pa程度)に保たれ、安定化させる。
次に、プラスチック容器8の内部に原料ガスを減圧された所定圧力下で吹き出させているときに、外部電極3に電源周波数5.5~6.5MHzの電力(例えば、6.0MHz)を供給する。この電力をエネルギー源として、プラスチック容器8内の原料ガスがプラズマ化される。これによって、プラスチック容器8の内壁面にDLC膜が成膜される。すなわち外部電極3に電源周波数5.5~6.5MHzの電力が供給されることによって、外部電極3と内部電極9との間でバイアス電圧が生ずると共にプラスチック容器8内の原料ガスがプラズマ化されて炭化水素系プラズマが発生し、DLC膜がプラスチック容器8の内壁面に成膜される。このとき、自動整合器26は、出力供給している電極全体からの反射波が最小になるように、インダクタンスL、キャパシタンスCによってインピーダンスを合わせている。
表1に500mlPETボトルにDLC膜を成膜したときの酸素バリア性を示した。この容器の酸素透過度は、Modern Control社製 Oxtran 2/20を用いて、23℃、90%RHの条件にて測定し、窒素ガス置換開始から72時間後の測定値(表1中、OTR値)を記載した。DLC膜の膜厚は、KLA tencor社製、Alpha-step iQを用いて測定したが、また、表2に280mlPETボトルにDLC膜を成膜したときの酸素バリア性を示した。表1及び表2において、BIF値とは、未コートボトルを基準として、酸素バリア性が何倍向上したかを示す値である。また、図3に表1と表2の結果をプロットした。
プラスチック容器の色の評価は着色度b*値を指標とした。b*値は、JISK 7105-1981の色差であり、三刺激値X,Y,Zから式1で求まる。
評価(ばらつき)×:x≧3
評価(ばらつき)△:0.5≦x<3
評価(ばらつき)○:x<0.5
表4において500mlPETボトルの「平均」は、平均着色度であり、次のとおりとした。肩部*b値と胴部*b値との平均値をxとしたとき、
評価(平均)×:x≧3
評価(平均)△:2.5≦x<3
評価(平均)○:x<2.5
評価(ばらつき)×:x≧1
評価(ばらつき)△:0.5≦x<1
評価(ばらつき)○:x<0.5
表5において280mlPETボトルの「平均」は、平均着色度であり、次のとおりとした。肩部*b値と胴部*b値との平均値をxとしたとき、
評価(平均)×:x≧4
評価(平均)△:3.5≦x<4
評価(平均)○:x<3.5
総合評価×:×+×、×+△(外観上問題あり)
総合評価△:×+○(従来品レベルである)
総合評価○:○+△(従来品の改良レベルである)
総合評価◎:○+○(呈色性が特に優れる)
表6に500mlPETボトルにDLC膜を成膜したときの密着性について評価した結果を示した。評価は、pH9の水酸化ナトリウム水溶液(0.01質量%)を65℃に保持し、容器を浸漬し、浸漬前(0日目)、1日浸漬(1日目)、2日浸漬(2日目)、3日浸漬(3日目)、4日浸漬(4日目)したときの膜の剥離を調べた。
○:剥離なし
△:長さ5mm未満の剥離片があり
×:長さ5mm以上の剥離片があり
○:剥離なし
△:長さ5mm未満の剥離片があり
×:長さ5mm以上の剥離片があり
表8に500mlPETボトルにDLC膜を成膜したときのカーボンダストの堆積について評価した。排気室内のほぼ中央部にあたる原料ガス導入管の外表面にシリコンウェハを設置し、成膜を10回行い、図1中、排気室内のFにおけるダストの堆積量(nm)を求めた。堆積量が多いほど、成膜装置の清掃間隔が短くなる。図6に電源周波数とカーボンダストの堆積量との関係を示した。
表9に500mlPETボトルにDLC膜を成膜したときの原料ガス導入管の質量変化を示した。ボトルのすぐ下流に位置する原料ガス導入管の外表面に着脱可能なステンレス製の筒状部材を設置し、成膜を100回行い、図1中の場所Eにおける当該部材の質量変化を調べ、評価をした。質量増加が大きいほど、ダスト堆積量が多いことを意味する。脱着時の誤差要因を考慮すると、2.5MHz~7MHzでは、有意な差はないと考えられる。一方、13.56MHzにおいては、有意に質量減少しており、これはプラズマの中心がボトルの口部近傍に存在したため、当該部材をエッチングしたためと考えられる。図7に500mlPETボトルにDLC膜を成膜したときの電源周波数とボトル口部近傍に設置した部材の質量変化との関係を示した。
表11に500mlPETボトルにDLC膜を成膜したときの、図1中、Dの箇所に設置した光センサの受光強度を示した。なお、当該Dは、ガス導入管中心から10cm離れた排気室外表面ののぞき窓である。受光強度はプラズマの発光強度と関係があり、受光強度が大きいほど、排気室にプラズマが近づいている若しくは排気室にてプラズマが発生している。結果的に受光強度が大きいほど、排気室内のプラズマ分布範囲が広く、かつプラズマ濃度が高いことになるため、排気室内の総ダスト堆積量が大きいことも意味する。同様に、表12に280mlPETボトルにDLC膜を成膜したときの、図1中、Dの箇所に設置した光センサの受光強度を示した。更に、図8に電源周波数と排気室における発光強度との関係を示した。
2 上部外部電極
3 外部電極(成膜ユニット)
4 絶縁部材
5 排気室
6 蓋
7 成膜ユニット
8 プラスチック容器(PETボトル)
9 内部電極(原料ガス供給管)
9a ガス吹き出し口
10,37,38 O-リング
11,14,17,21 配管
12,18,22,真空バルブ
13 マスフローコントローラー
15 原料ガス発生源
16 原料ガス供給手段
19 リーク源
20 圧力ゲージ
23 真空ポンプ
24 排気ダクト
26 自動整合器(マッチングボックス,M.BOX)
27 プラズマ発生用電源
30 外部電極(成膜ユニット)の内部空間
31 排気室の内部空間
32,32a,32b 開口部
35 プラズマ発生用電力供給手段
100 成膜装置
Claims (7)
- 成膜ユニットとなる外部電極にプラスチック容器を収容する工程と、
前記プラスチック容器の内部に原料ガス供給管となる内部電極を配置する工程と、
真空ポンプを作動させて前記外部電極の内部のガスを排気する工程と、
前記プラスチック容器の内部に原料ガスを減圧下で吹き出させる工程と、
前記外部電極に電力を供給するプラズマ発生用電源の電源周波数を5.5~6.5MHzに設定し、前記原料ガスをプラズマ化して、前記プラスチック容器の内壁面にガスバリア性を有する薄膜を成膜する工程と、
を有することを特徴とするガスバリア性薄膜コーティングプラスチック容器の製造方法。 - 前記プラスチック容器を前記外部電極に収容する工程において、容器の口部を下方に向けた状態で収容することを特徴とする請求項1に記載のガスバリア性薄膜コーティングプラスチック容器の製造方法。
- 前記プラスチック容器の内部に原料ガス供給管となる内部電極を配置する工程において、容器の高さをhとし、容器の底を基準点としたとき、前記原料ガス供給管の先端が、1/2・h以上2/3・h以下の範囲の位置にあるように、前記原料ガス供給管が容器の口部から挿入されていることを特徴とする請求項1又は2に記載のガスバリア性薄膜コーティングプラスチック容器の製造方法。
- 内部空間が有底円筒形である外部電極を使用することを特徴とする請求項1、2又は3に記載のガスバリア性薄膜コーティングプラスチック容器の製造方法。
- ガスバリア性薄膜として、炭素膜、珪素含有炭素膜又は金属酸化物膜を成膜することを特徴とする請求項1、2、3又は4に記載のガスバリア性薄膜コーティングプラスチック容器の製造方法。
- 前記プラスチック容器は、容量が500ml以上の容器であることを特徴とする請求項1、2、3、4又は5に記載のガスバリア性薄膜コーティングプラスチック容器の製造方法。
- 前記プラスチック容器がポリエチレンテレフタレート製容器であることを特徴とする請求項1、2、3、4、5又は6に記載のガスバリア性薄膜コーティングプラスチック容器の製造方法。
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CN2009801586671A CN102395706B (zh) | 2009-04-13 | 2009-06-25 | 阻气性薄膜涂层塑料容器的制造方法 |
BRPI0924233A BRPI0924233A2 (pt) | 2009-04-13 | 2009-06-25 | método para produzir um recipiente plástico revestido por filme fino de barreira aos gases |
SG2011074614A SG175202A1 (en) | 2009-04-13 | 2009-06-25 | Method for manufacturing gas barrier thin film-coated plastic container |
KR1020117026912A KR101357325B1 (ko) | 2009-04-13 | 2009-06-25 | 가스 배리어성 박막 코팅 플라스틱 용기의 제조 방법 |
US13/264,079 US8883257B2 (en) | 2009-04-13 | 2009-06-25 | Method for manufacturing gas barrier thin film-coated plastic container |
AU2009344573A AU2009344573B2 (en) | 2009-04-13 | 2009-06-25 | Method for manufacturing gas barrier thin film-coated plastic container |
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PCT/JP2009/061582 WO2010119578A1 (ja) | 2009-04-13 | 2009-06-25 | ガスバリア性薄膜コーティングプラスチック容器の製造方法 |
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US (1) | US8883257B2 (ja) |
EP (1) | EP2420592B1 (ja) |
JP (1) | JP4372833B1 (ja) |
KR (1) | KR101357325B1 (ja) |
CN (1) | CN102395706B (ja) |
BR (1) | BRPI0924233A2 (ja) |
MY (1) | MY153131A (ja) |
SG (1) | SG175202A1 (ja) |
WO (1) | WO2010119578A1 (ja) |
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DE102010000983A1 (de) * | 2010-01-18 | 2011-07-21 | Joanneum Research Forschungsges. M.B.H. | Plasma- bzw. ionengestützes System zur Herstellung haftfester Beschichtungen auf Fluorpolymeren |
JPWO2011152182A1 (ja) * | 2010-05-31 | 2013-07-25 | 株式会社ジェイテクト | 被覆部材の製造方法 |
JP5643605B2 (ja) * | 2010-10-27 | 2014-12-17 | サントリーホールディングス株式会社 | 測定装置および測定方法 |
US9404334B2 (en) | 2012-08-31 | 2016-08-02 | Baker Hughes Incorporated | Downhole elastomeric components including barrier coatings |
TWI551712B (zh) | 2015-09-02 | 2016-10-01 | 財團法人工業技術研究院 | 容器內部鍍膜裝置及其方法 |
US10337105B2 (en) * | 2016-01-13 | 2019-07-02 | Mks Instruments, Inc. | Method and apparatus for valve deposition cleaning and prevention by plasma discharge |
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JPH0372269B2 (ja) | 1988-02-16 | 1991-11-18 | Misuzu Tofu Kk | |
JP2788412B2 (ja) | 1994-08-11 | 1998-08-20 | 麒麟麦酒株式会社 | 炭素膜コーティングプラスチック容器の製造装置および製造方法 |
JP3072269B2 (ja) * | 1997-02-19 | 2000-07-31 | 麒麟麦酒株式会社 | 炭素膜コーティングプラスチック容器の製造装置および製造方法 |
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WO1995022413A1 (en) * | 1994-02-16 | 1995-08-24 | The Coca-Cola Company | Hollow containers with inert or impermeable inner surface through plasma-assisted surface reaction or on-surface polymerization |
EP1010773A4 (en) | 1997-02-19 | 2004-08-25 | Kirin Brewery | METHOD AND DEVICE FOR PRODUCING PLASTIC CONTAINER COATED WITH CARBON FILM |
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2009
- 2009-04-13 JP JP2009097494A patent/JP4372833B1/ja active Active
- 2009-06-25 EP EP09843356.8A patent/EP2420592B1/en active Active
- 2009-06-25 CN CN2009801586671A patent/CN102395706B/zh active Active
- 2009-06-25 SG SG2011074614A patent/SG175202A1/en unknown
- 2009-06-25 WO PCT/JP2009/061582 patent/WO2010119578A1/ja active Application Filing
- 2009-06-25 US US13/264,079 patent/US8883257B2/en active Active
- 2009-06-25 KR KR1020117026912A patent/KR101357325B1/ko active IP Right Grant
- 2009-06-25 MY MYPI20114822 patent/MY153131A/en unknown
- 2009-06-25 BR BRPI0924233A patent/BRPI0924233A2/pt not_active IP Right Cessation
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JPH0372269B2 (ja) | 1988-02-16 | 1991-11-18 | Misuzu Tofu Kk | |
JP2788412B2 (ja) | 1994-08-11 | 1998-08-20 | 麒麟麦酒株式会社 | 炭素膜コーティングプラスチック容器の製造装置および製造方法 |
JP3072269B2 (ja) * | 1997-02-19 | 2000-07-31 | 麒麟麦酒株式会社 | 炭素膜コーティングプラスチック容器の製造装置および製造方法 |
JP4188315B2 (ja) | 2002-05-28 | 2008-11-26 | 麒麟麦酒株式会社 | Dlc膜コーティングプラスチック容器及びその製造装置 |
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JP2008088471A (ja) | 2006-09-29 | 2008-04-17 | Mitsubishi Shoji Plast Kk | ガスバリア性プラスチック容器の製造装置及びその製造方法 |
JP2008088472A (ja) | 2006-09-29 | 2008-04-17 | Mitsubishi Shoji Plast Kk | ガスバリア性プラスチック容器の製造装置及びその製造方法 |
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SG175202A1 (en) | 2011-11-28 |
EP2420592A4 (en) | 2013-09-25 |
US20120052215A1 (en) | 2012-03-01 |
BRPI0924233A2 (pt) | 2016-01-26 |
KR101357325B1 (ko) | 2014-02-03 |
AU2009344573A1 (en) | 2011-11-03 |
US8883257B2 (en) | 2014-11-11 |
JP4372833B1 (ja) | 2009-11-25 |
CN102395706B (zh) | 2013-07-24 |
EP2420592B1 (en) | 2014-10-15 |
MY153131A (en) | 2014-12-31 |
JP2010248549A (ja) | 2010-11-04 |
CN102395706A (zh) | 2012-03-28 |
EP2420592A1 (en) | 2012-02-22 |
KR20120012467A (ko) | 2012-02-09 |
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