JP4279127B2 - Gas barrier thin film coated plastic container manufacturing apparatus and manufacturing method thereof - Google Patents

Description

  The present invention relates to an apparatus for manufacturing a plastic container whose outer surface is coated with a gas barrier thin film such as an amorphous hydrocarbon film and a method for manufacturing the container.

  As a technique for improving the gas barrier property of a plastic container, there is a method of coating a hydrogenated amorphous carbon film (hereinafter referred to as DLC (Diamond Like Carbon)) on the inner wall surface of the plastic container. A technique relating to a manufacturing apparatus and a manufacturing method thereof has been disclosed (see, for example, Patent Document 1).

  The DLC thin film has excellent gas barrier properties such as oxygen gas and carbon dioxide gas, and also prevents the adsorption of flavor components and various chemical components to the plastic and the elution of foreign materials and impurities in the plastic into the contents. Excellent in terms. It is particularly suitable for use in plastic containers that are washed repeatedly.

  However, at present, in the case of a beverage container, the case where it is used as a so-called disposable (one-way) container in which a plastic container is not used repeatedly is particularly popular because of its convenience to consumers.

  Even in this case, a beverage sensitive to oxygen requires a considerable gas barrier property, so that a PET (polyethylene terephthalate resin) bottle as a plastic container for beverages may be insufficient. is there. In this case, development and practical application of bottle technologies aimed at improving gas barrier properties such as the aforementioned DLC coating bottles and multilayer bottles in which a resin excellent in gas barrier properties is sandwiched between PET resins are being actively carried out.

  Among these, DLC coating technology seems to be one step ahead in terms of performance, cost, and recyclability, but gas barrier properties can also be obtained by coating the outer surface of a plastic container with DLC thin film, and the inner surface of the container. Compared with the case where the film is formed, the work cost for film quality control and safety evaluation can be reduced. Therefore, the film is formed on the outer surface as well as the bottle formed with the DLC thin film on the inner surface of the container. There is also a great demand for bottles.

  However, when the DLC thin film is formed on the outer surface of the PET bottle using electromagnetic CVD, the surface of the base material is opposite to the surface of the base material (the outer surface of the bottle) to be coated with the internal electrode. If it is not installed within a few millimeters, good film quality and adhesion cannot be obtained, so in the case of a shape in which the inner diameter of the body is larger than the opening diameter of the mouth, such as a bottle, such an electrode is placed inside It is difficult to put in.

  In such a situation, several techniques for coating a gas barrier thin film on the outer surface of a container have been disclosed. The method of coating the outer surface of the container with a silicon oxide thin film (see, for example, Patent Document 2 and Patent Document 3) cannot provide a strong gas barrier thin film on the outer surface of the container, and the gas barrier property can be improved by several times. is there. Moreover, it is not certain whether the DLC on the outer surface of the bottle is selectively deposited by a method (see, for example, Patent Document 4) in which DLC can be coated on the inner surface and the outer surface of the bottle by microwave CVD.

JP-A-8-53117 US4478874 WO98 / 40531 WO99 / 49991

  The present inventors consider that the gas barrier property is improved only about several times because the gas barrier thin film is not formed on the surface of the container in a state where the original performance can be sufficiently exerted in the above prior art method. Further, even if a thin film is formed on plastic, it is not formed with a sufficient self-bias voltage applied, so that the adhesion strength is not sufficient, and it is considered that the gas barrier property is not improved due to easy peeling.

  Therefore, an object of the present invention is to fill a container with an electrolyte as a high-frequency power conductive medium when forming a gas barrier thin film on the outer surface of a plastic container by a low pressure plasma CVD method, A film forming device that can sufficiently apply a self-bias voltage to the outer surface of a plastic container so that the thin film functions as a gas barrier thin film by causing the electrolyte to play the same role as inserting an electrode having the same shape as the shape Is to provide.

  The object of the present invention is not only the above-mentioned low pressure plasma CVD method, but also an atmospheric pressure plasma CVD method, in which the container is filled with an electrolyte as a conductive medium for electromagnetic power, and a self-bias voltage is sufficiently applied to the outer surface of the plastic container. An object of the present invention is to provide a film forming apparatus in which the formed thin film can function as a gas barrier thin film. The atmospheric pressure plasma CVD method does not require a depressurization step, and the time required for forming a film on one plastic container can be shortened, so that productivity can be improved and the vacuum system of the apparatus can be improved. Costs required can be reduced.

  It is a further object of the present invention to provide an apparatus capable of coping with a plastic container having a small diameter while reducing the number of parts of the apparatus by combining an electrolyte injection tube and an internal electrode.

  Another object of the present invention is to provide an apparatus for forming a gas barrier thin film on a portion below the neck ring without forming a film on the mouth. Since the mouth has a large thickness, the gas barrier property of the plastic itself is higher than other parts, so there is little need for a gas barrier thin film, and the film-forming part and the non-film-forming part are separated from the neck ring. Better aesthetics of the bottle.

  Furthermore, the present invention serves as an internal electrode by serving as a liquid such as beer, wine, fruit juice beverage, tea-based beverage, carbonated beverage or sports beverage, in which a plastic container is filled with an electrolytic solution. It is intended to provide a manufacturing apparatus capable of functioning as a plasma-exciting power conducting medium and incorporating a beverage filling process into a film forming process and simultaneously performing the process to save labor.

  The present invention relates to a manufacturing apparatus for forming a DLC thin film, a silicon oxide thin film such as SiOx, or a silicon-containing DLC thin film such as a C—Si—H thin film or a C—Si—H—O thin film as a gas barrier thin film. The purpose is to provide.

  Further, according to the present invention, the volume of the internal electrode in the portion immersed in the electrolytic solution, the volume of the electrolytic solution injection tube, or the volume of the internal electrode also serving as the electrolytic solution injection tube is substantially the same volume as the head space under the neck ring. Thus, a device capable of forming a dense gas barrier thin film by raising the liquid level of the electrolyte during film formation to the vicinity of the neck ring and sufficiently applying a self-bias voltage to the container from the bottom of the container to the height when the liquid level is raised. The purpose is to provide.

  In the present invention, when a gas barrier thin film is formed on the outer surface of a plastic container, the container is filled with an electrolyte as a conductive medium for plasma excitation power, and an electrode having the same shape as the inner surface of the container is filled in the inner space of the container. By providing the electrolyte with the same role as the case of inserting a film, it is possible to provide a film forming method capable of sufficiently applying a self-bias voltage to the outer surface of the plastic container so that the thin film functions as a gas barrier thin film. . At this time, a film forming method by a low pressure plasma CVD method and a film forming method by an atmospheric pressure plasma CVD method are provided. In particular, in a film forming method using a low-pressure plasma CVD method, an object is to provide a pre-evacuation step in a plastic container, that is, a filling method that prevents contamination of oxygen as much as possible when filling an electrolytic solution. And Conventionally, the pre-evacuation process is a technique that can only be applied to filling a glass bottle.

  As a result of diligent research to achieve the above-mentioned object and to make use of the advantages of a gas barrier thin film such as a DLC thin film having high gas barrier properties, the inventors have brought the electrolyte solution filled in the bottle close to the bottle surface inside the plastic bottle. As a result, the inventors have found that a technique for coating a gas bottle thin film such as a DLC thin film on the outer surface of a plastic bottle has been found.

  That is, the apparatus for producing a gas barrier thin film coating container according to the present invention has a housing space that can accommodate almost the whole or the entire container except the mouth of the plastic container, and the gas in the housing space is contained in the inner space of the plastic container. A vacuum chamber that also serves as an external electrode that accommodates and holds the plastic container so as not to flow in, an electrolyte injection tube that is detachably disposed inside the plastic container and fills the plastic container with an electrolyte, and An internal electrode that is detachably disposed inside the plastic container so as to come into contact with the electrolytic solution when the plastic container is filled with the electrolytic solution, and a high-frequency supply that supplies high-frequency power to the internal electrode or the external electrode Means, vacuum means for depressurizing the outside of the plastic container in the housing space, and plasma to gas barrier properties Characterized in that it comprises a source gas supply means for supplying to the outside of the plastic container of the feed gas the accommodating space for forming a film on the outer surface of the plastic container.

  Further, the gas barrier thin film coating container manufacturing apparatus according to the present invention has a storage space that can be accommodated so that there is a gap enough to generate plasma in the entire container or the entire container excluding the mouth of the plastic container. A chamber that also serves as an external electrode that accommodates and holds the plastic container so that the gas in the housing space does not flow into the inner space of the plastic container, and is detachably disposed in the plastic container, and an electrolytic solution is provided in the plastic container. An electrolyte injection tube that fills the plastic container, an internal electrode that is detachably disposed in the plastic container so as to come into contact with the electrolyte when the plastic container is filled with the electrolyte, and the internal electrode or the Electromagnetic wave supplying means for supplying electromagnetic power to the external electrode, and plasma forming the gas barrier thin film by converting it into plasma under atmospheric pressure Characterized in that the raw material gas for forming the outer surface of the vessel with an inert gas and a source gas supply means for supplying to the outside of the plastic container of the accommodating space. At this time, it is more preferable to provide a gas replacement means for replacing the inside of the housing space with a source gas containing an inert gas.

  Here, in the gas barrier thin film coating container manufacturing apparatus according to the present invention, it is preferable that the internal electrode has a tube shape and is also used as the electrolyte solution injection tube. It is possible to provide a device that can reduce the number of parts of the device and can cope with a plastic container having a small diameter.

  In the gas barrier thin film coating container manufacturing apparatus according to the present invention, a nozzle seal that penetrates the internal electrode and seals the mouth of the plastic container is provided, and the plastic container is further disposed in the vacuum chamber or the chamber. When holding, it is preferable to seal the neck ring of the plastic container so as to obtain airtightness.

  Furthermore, in the apparatus for manufacturing a gas barrier thin film coating container according to the present invention, the electrolyte also serves as a liquid to be filled in a plastic container, and plasma is applied when plasma excitation power is applied to the internal electrode or the external electrode. It is preferable to use a power conduction medium for excitation.

  In the apparatus for producing a gas barrier thin film coating container according to the present invention, it is preferable that the electrolytic solution is beer, wine, fruit juice beverage, tea-based beverage, carbonated beverage or sports beverage. By serving as a liquid (beverage) that fills the plastic container with the electrolytic solution, it functions as a plasma-exciting power conduction medium that plays the same role as the internal electrode, and at the same time incorporates the beverage filling process into the film forming process. This makes it possible to save labor in the process.

  In the apparatus for manufacturing a gas barrier thin film coating container according to the present invention, the source gas is a gas containing a carbon compound as a main component, a gas containing an organosilicon compound as a main component, or a carbon compound and A gas mainly composed of a mixed gas with an organosilicon compound is preferred. As the gas barrier thin film, a DLC thin film, a silicon oxide thin film such as SiOx, or a silicon-containing DLC thin film such as a C—Si—H-based thin film or a C—Si—H—O-based thin film can be used.

  Furthermore, in the apparatus for manufacturing a gas barrier thin film coating container according to the present invention, the volume of the internal electrode or the volume of the electrolyte injection pipe in the portion immersed in the electrolyte or the electrolyte injection pipe according to claim 3 is also used. The volume of the internal electrode is preferably substantially the same as the head space under the neck ring. By adjusting the liquid level of the electrolytic solution during film formation, uniform film formation up to the neck ring can be performed.

  The method for producing a gas barrier thin film-coated plastic container according to the present invention comprises that the whole or the entire container excluding the mouth of the plastic container is placed in a vacuum chamber that also serves as an external electrode, and the inside of the plastic container from the vacuum chamber. The plastic container is filled and held with an electrolyte so that gas does not flow into the space, and an internal electrode is disposed in the plastic container so as to contact the electrolyte, and the plastic in the vacuum chamber After supplying the raw material gas of the gas barrier thin film into the decompression space using the outside of the container as the decompression space, high frequency power is applied to the internal electrode or the external electrode to make the raw material gas into plasma, and the outside of the plastic container A gas barrier thin film is formed on the surface. At this time, before filling the plastic container with the electrolyte solution, the plastic container is evacuated and further carbon dioxide or nitrogen gas is supplied to replace the gas to remove residual oxygen in the plastic container. And it is preferable that the outside of the plastic container in the vacuum chamber is in a decompressed state so that the plastic container is not crushed when the inside of the plastic container is evacuated. This is a new filling method including a pre-evacuation process for preventing the mixing of oxygen as much as possible when filling the electrolytic solution in the plastic container. Thereby, it becomes possible to preserve | save a drink sensitive to oxygen for a long time by the synergistic effect with coating the outer surface of a container with a gas-barrier thin film.

  Further, the method for producing a gas barrier thin film coated plastic container according to the present invention includes a chamber that also serves as an external electrode, and a gap that allows plasma to be generated in the entire chamber or the entire container except for the mouth of the plastic container. Storing and holding gas so as not to flow into the inner space of the plastic container from the inside, filling the plastic container with an electrolytic solution and disposing an internal electrode inside the plastic container so as to contact the electrolytic solution, A source gas of a gas barrier thin film is supplied together with an inert gas to the outside of the plastic container in the chamber, and electromagnetic power is applied to the internal electrode or the external electrode so that the source gas is turned into plasma at atmospheric pressure. A gas barrier thin film is formed on the outer surface of the plastic container. At this time, after replacing the raw material gas of the gas barrier thin film together with an inert gas outside the plastic container in the chamber, electromagnetic wave power is applied to the internal electrode or the external electrode to supply the raw material gas. It is more preferable that the gas barrier thin film is formed on the outer surface of the plastic container by converting it into plasma under atmospheric pressure.

  The film forming apparatus according to the present invention, when forming a gas barrier thin film on the outer surface of a plastic container, fills the container with an electrolytic solution as a conductive medium for electromagnetic power such as high-frequency power, and places the container in the inner space of the container By allowing the electrolyte to play the same role as inserting an electrode with the same shape as the inner surface shape, it is possible to sufficiently apply a self-bias voltage to the outer surface of the plastic container. Could function as. Film formation can be performed not only by a low pressure plasma CVD method but also by a normal pressure plasma CVD method according to the same principle. In particular, the atmospheric pressure plasma CVD method does not require a depressurization step, and the time required for forming a film on one plastic container can be shortened, so that productivity can be improved and the apparatus can be simplified. In addition, the cost required for the vacuum system of the apparatus can be reduced.

  The method for manufacturing a gas barrier thin film-coated plastic container according to the present invention includes the steps of filling a container with an electrolyte as a conductive medium for plasma excitation power when forming a gas barrier thin film on the outer surface of the plastic container. Self-bias voltage is applied to the outer surface of the plastic container so that the thin film functions as a gas barrier thin film by causing the electrolyte to play the same role as when an electrode having the same shape as the inner surface of the container is inserted into the inner space of the container. Can be applied sufficiently.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to these descriptions.

(First embodiment: a manufacturing apparatus using a low pressure plasma CVD method)
FIG. 1 shows a schematic configuration diagram of an embodiment of an apparatus for producing a gas barrier thin film coated plastic container by a low pressure plasma CVD method. In FIG. 1, the vacuum chamber is a schematic sectional view. The manufacturing apparatus according to the present embodiment has an accommodation space 15 that can accommodate almost the entire container except the mouth of the plastic container 1 or the entire container so that the gas in the accommodation space 15 does not flow into the inner space of the plastic container 1. A vacuum chamber 16 that also serves as an external electrode that accommodates and holds the plastic container 1, an electrolyte injection pipe 3 that is detachably disposed inside the plastic container 1 and fills the plastic container 1 with an electrolyte, and a plastic container 1 An internal electrode 3 that is removably disposed inside the plastic container 1 so as to come into contact with the electrolytic solution when filled with the electrolytic solution (this figure shows a configuration also used as the electrolytic solution injection tube 3) A high-frequency supply means 7 for supplying high-frequency power to the internal electrode 3; a vacuum means 8 for depressurizing the outside of the plastic container 1 in the housing space 15 of the vacuum chamber 16; The gas barrier thin film and a raw material gas supply means 10 for supplying to the outside of the plastic container 1 out of the housing space 15 of the raw material gas for forming the outer surface of the plastic container 1.

  The vacuum chamber 16 includes a chamber body 2 made of a conductor and a lid 13 that holds a plastic container. An O-ring 4 is disposed between the chamber body 2 and the lid 13 to ensure airtightness. By configuring the vacuum chamber 16 with the chamber body 2 and the lid 13, the opening of the chamber body 2 serves as an accommodation port for accommodating the plastic container 1 in the vacuum chamber 16. The vacuum chamber is strong enough to withstand vacuum decompression. Furthermore, the vacuum chamber needs to be kept completely airtight with a seal at the bottle mouth from the inner space of the plastic container. The lid 13 may be either a conductor or an insulator, and for easy setting of the plastic container 21, the lid 13 may be appropriately divided while ensuring hermeticity. The lid 13 is provided with an opening so that the mouth of the plastic container 1 can be inserted in an airtight state, and an O-ring 4 is disposed between the container mouth and the opening. Here, by allowing the lid to be divided, the container may be fitted in the opening of the lid 13 in the vicinity of the neck ring 14 with good airtightness as shown in FIG. Further, the chamber body 2 may be divided vertically or horizontally to facilitate setting of the plastic container, and is preferably grounded. Inside the vacuum chamber 16, there is formed an accommodation space 15 having a size capable of accommodating almost the entire container except the mouth of the plastic container 1 or the entire container, and the plastic container is accommodated in this accommodation space during film formation. The In the case of FIG. 1, the shape of the accommodation space 15 is a cylindrical shape, but other shapes may be employed. Further, the housing space 15 may be a space that can contain not only one plastic container but also two or more. In any case, the shape of the storage space 15 is such that plasma can be generated outside the plastic container 1 in the storage space 15, and each location on the outer surface of the container when high frequency power is supplied to the internal electrode 3. Any shape can be used as long as an appropriate self-bias voltage can be applied. However, since the space for generating plasma is a decompressed space, it is not necessary to make it larger than necessary from the viewpoint of exhaust efficiency, that is, production efficiency. In FIG. 1, the plastic container 1 is accommodated in the accommodation space 15 except for the mouth portion, which is because a gas barrier thin film is not formed on the outer surface of the mouth portion. At this time, the vacuum chamber 16 holds the plastic container 1 with the lid 13, but it is preferable to seal the neck ring 14 of the plastic container 1 with an O-ring so as to obtain airtightness. When a gas barrier thin film is formed on the outer surface of the mouth, the entire container is accommodated in the accommodating space 15. At this time, the container is sealed with the top of the mouth so that no gas is mixed into the container.

  The electrolyte solution injection tube 3 has a hollow tube shape and is detachably disposed inside the plastic container 1 to fill the plastic container 1 with the electrolyte solution. The electrolytic solution is sent from the electrolytic solution supply means 11 to the electrolytic solution injection tube 3. Although the electrolyte injection tube and the internal electrode may be provided separately, it is preferable that the electrolyte injection tube 3 also serves as the internal electrode as shown in FIG. This is because it is possible to cope with a case where the diameter of the mouth of the container is small, and the number of parts of the apparatus can be reduced. When the electrolyte injection tube is separated from the internal electrode, it may be a conductor or a non-conductor. In the case of sharing, a conductor such as a stainless steel tube is used. At the lower end of the electrolyte injection tube 3, one electrolyte solution blowout hole for communicating the inside and outside of the electrolyte injection tube 3 is formed.

  The internal electrode 3 needs to be in contact with, or preferably inserted into, the electrolytic solution in order to apply high-frequency power to the bottle filled with the electrolytic solution. The internal electrode 3 is supplied with high frequency power from the high frequency supply means 7. The manufacturing apparatus preferably includes a nozzle seal 5 that penetrates the internal electrode 3 and seals the mouth of the plastic container 1, including the case where the internal electrode and the electrolyte solution injection tube are used together. Here, there is usually no replacement process for filling a PET bottle, and gas replacement is performed by the same process (gassing) as a can. At this time, it is preferable that the top surface of the container mouth and the nozzle seal 5 are sealed, and the pressure difference between the injection pressure and the pressure in the container is adjusted in order to prevent bubbling of the electrolyte when filling the electrolyte. . Further, the electrolytic solution may be injected so that air is not mixed by a method of reducing the pressure while adjusting the external pressure and the internal pressure so that the bottle is not deformed. That is, before filling the plastic container with the electrolytic solution, the plastic container is evacuated and further carbon dioxide gas or nitrogen gas is supplied to replace the gas to remove residual oxygen in the plastic container. At this time, it is preferable that the outside of the plastic container in the vacuum chamber is in a decompressed state so that the plastic container is not crushed when the plastic container is evacuated. Such a filling method is a filling method including a pre-evacuation process for preventing the mixing of oxygen as much as possible when filling the electrolytic solution. However, the filling method can be applied to a plastic container for the first time by the present invention. Here, a synergistic effect with the coating of the gas barrier thin film on the outer surface of the container is expected, and it becomes possible to store a drink sensitive to oxygen for a longer time. In the pre-evacuation process, two or more gas replacements may be performed in addition to the one gas replacement. The material of the internal electrode 3 is preferably stainless steel (SUS) or aluminum.

  The high frequency supply means 7 includes a matching box (not shown) connected to the internal electrode 3 and a high frequency power source (not shown) for supplying a high frequency to the matching box. A matching box is connected to the output side of the high frequency power supply. The high frequency power source is grounded. The high-frequency power source generates a high-frequency voltage between the ground potential and the high-frequency voltage is applied between the internal electrode 3 and the chamber body 2 or between the internal electrode 3 and the vacuum chamber 16. As a result, the source gas is turned into plasma outside the plastic container 1 in the accommodation space 15. The frequency of the high-frequency power source is 100 kHz to 1000 MHz, and for example, an industrial frequency of 13.56 MHz is used.

  The nozzle seal 5 is connected to the exhaust means 9 and is in contact with the top of the container mouth so as to maintain airtightness with an O-ring so that the inside of the container can be decompressed. The exhaust means 9 is for adjusting the differential pressure between the electrolyte injection pressure and the container internal pressure as described above.

  The source gas supply means 10 introduces source gas supplied from a source gas generation source (not shown) outside the plastic container 1 in the accommodation space 15. The source gas supply means 10 is preferably configured in the order of a source gas generation source (not shown), a mass flow controller (not shown), and a vacuum valve (not shown). The vacuum valve (not shown) is connected to the lid 13 by piping. Is done. In FIG. 1, the source gas supply means 10 is connected to the lid 13, but it may be connected to the chamber body 2. However, when the air cylinder 6 is provided in the chamber main body 2 as shown in FIG. 1 to provide an elevating function, it is preferable to connect the raw material gas supply means 10 to a fixable lid 13.

  The vacuum means 8 evacuates the outside of the plastic container 1 in the housing space 15 and is used to form a decompression space for performing gas substitution from the air to the source gas and performing the decompression plasma CVD method. In order to shorten the evacuation time, it is preferable to maintain a high exhaust conductance without forming a narrow air passage. This reduced pressure is, for example, 5 to 15 Pa before introducing the source gas and 7 to 22 Pa at the time of film formation.

  The vacuum means 8 and the exhaust means 9 are formed by a vacuum valve (not shown), an exhaust pump (not shown), and piping connecting them.

  In the present invention, the container includes a container that is used with a lid, a stopper, or a seal, or a container that is used without being used. The size of the opening is determined according to the contents. The plastic container includes a plastic container having a predetermined thickness having moderate rigidity and a plastic container formed by a sheet material having no rigidity. Moreover, either a returnable container or a one-way container may be used.

  Resin used when molding the plastic container of the present invention is polyethylene terephthalate resin (PET), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin (PP), cycloolefin copolymer resin (COC, 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, polyvinylidene chloride resin, polyamide resin, Polyamideimide resin, polyacetal resin, polycarbonate resin, polysulfone resin, or tetrafluoroethylene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin It can Shimesuru. Among these, PET is particularly preferable.

  The source gas is preferably a gas mainly composed of a carbon compound, a gas mainly composed of an organosilicon compound, or a gas composed mainly of a mixed gas of a carbon compound and an organosilicon compound. For example, the following can be illustrated. Among the carbon compounds, examples of the hydrocarbon gas include alkanes such as methane, ethane, propane, butane, pentane and hexane, alkenes such as ethylene, propylene, butene, pentene and butadiene, alkynes such as acetylene, and benzene. Aromatic hydrocarbons such as toluene, xylene and naphthalene, cycloparaffins such as cyclopropane and cyclohexane, and cycloolefins such as cyclopentene and cyclohexene can be used. In addition to the hydrocarbon gas, oxygen-containing carbon compound gases such as methyl alcohol and ethyl alcohol, and nitrogen-containing hydrocarbon gases such as methylamine, ethylamine, and aniline may be used. Carbon monoxide and carbon dioxide can also be used. Further, these gases may be used alone, but they may be mixed, and further mixed with a rare gas such as helium or argon. Among inert gases, noble gases include helium, argon, neon, xenon, etc. as gases composed of Group 0 elements of the periodic table. These may be used alone or in combination of two or more. Also good. In this case, the treatment may be performed in the presence of nitrogen or the like.

In addition, by replacing the DLC thin film with a raw material gas such as an organic silicon compound gas (such as a silane compound) or a mixed gas of an organic silicon compound gas and a carbon compound gas, a silicon oxide thin film or a silicon oxide-amorphous hydrocarbon is obtained. A composite membrane can also be used. When forming a silicon oxide gas barrier thin film such as SiOx, an organic silicon compound is used as a raw material. When a silicon-containing DLC film is formed, a Si-containing hydrocarbon-based gas is used, or a carbon compound gas and an organic silicon compound gas are mixed to form a film. Examples of organosilicon compounds include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethoxysilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propylsilane. , Phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. 1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, and octamethylcyclotetrasiloxane are preferred. However, it is not limited to these, Aminosilane, silazane, etc. can also be used. Note that a source gas such as a gas mainly containing a carbon compound, a gas mainly containing an organosilicon compound, or a mixed gas thereof is preferably used as a gas or a vapor. That is, if the carbon compound or organosilicon compound is in a gaseous state, it is transported as it is, and if it is liquid at room temperature, it is heated and vaporized and transported with an inert gas or bubbled with an inert gas and transported. Use. Further, a solid material at room temperature is heated and vaporized and conveyed by an inert gas. Moreover, the raw material for vaporization may promote vaporization in a reduced pressure state. Further, a gas mixed with oxygen or a gas having an oxidizing power (for example, N ₂ O, CO _2, etc.), a gas obtained by mixing the above mixed gas with helium and / or argon as an inert gas, or nitrogen, fluoride A raw material gas can also be obtained by appropriately adding carbon or the like.

When a carbon compound gas is used, a DLC thin film is formed. In this embodiment, the DLC film is a carbon film called an i-carbon film or a hydrogenated amorphous carbon film (a-CH), which is an SP ³ bond. An amorphous carbon film containing The DLC film has a film quality ranging from hard to soft (polymer-like), and the hydrogen content ranges from about 0 to 70 atom% (atomic%).

  The electrolyte in the present embodiment is in an ionized state when electromagnetic power such as high-frequency power is applied to the internal electrode 3, and functions as a plasma excitation power, that is, a conductive medium for electromagnetic power including high-frequency power. Is. The electrolyte can also serve as a liquid to be filled in a plastic container. In an actual plastic bottled beverage production process, the electrolyte is a beverage (water has a large dielectric constant of about 80, so the ionization of the electrolyte Beer, wine, fruit juice drinks, carbonated drinks, tea drinks, sports drinks, etc. all function effectively as a conduction medium for plasma excitation power.) It can be done at the same time. Of course, before filling the beverage, it is also possible to fill the bottle with an electrolytic solution (such as saline) and coat it as a pre-process. Since the electrolyte functions as a conductive medium for electromagnetic power, the combination of the internal electrode and the electrolyte exhibits an electrode function equivalent to that of an electrode having the same shape as the inner surface of the plastic container. A negative self-bias voltage can be sufficiently applied to the outer surface of the container. By this self-bias voltage, a so-called sputtering effect is obtained in which source gas ions that have been converted into plasma are attracted and collide with the outer surface of the plastic container. Thereby, the thin film is sufficiently adhered to the plastic, and the thin film exhibits the original gas barrier property as a gas barrier thin film.

  In the first embodiment, the high frequency supply means 7 supplies high frequency power to the internal electrode 3 as shown in FIG. However, the high-frequency supply means 7 may be configured to supply high-frequency power to the external electrode that also serves as the vacuum chamber 16. In FIG. 4, the form which connected the high frequency supply means 7 to the chamber main body 2 which is a conductor was shown. In this case, it is considered that a potential difference is generated between the housing space 15 and the outer surface of the container which is the ground potential, and the source gas that has been formed into a plasma by the potential difference is attracted to the outer surface of the container, so A thin film is formed.

(Second embodiment: Manufacturing apparatus using atmospheric pressure plasma CVD method)
As described above, one embodiment of the film forming apparatus using the low pressure plasma CVD method has been described with reference to FIG. 1. However, according to the present invention, the coating can be performed at atmospheric pressure or under a considerably low vacuum (about a fraction of atmospheric pressure). Is possible. In other words, atmospheric pressure plasma is generated by applying electromagnetic wave voltage, and the source gas is turned into plasma and deposited on the outer surface of the bottle, or between the electrolyte electrode in the bottle and the grounded external electrode, the source gas and argon gas, nitrogen gas, etc. It is also possible to coat by atmospheric pressure plasma CVD with an inert gas. Here, the purpose of mixing the inert gas into the source gas is mainly to adjust the concentration of the source gas. In this case, compared with the first embodiment, the depressurization step is not required, so that the production efficiency is improved during mass production. This embodiment follows the atmospheric pressure plasma CVD method as shown in FIG. FIG. 2 shows a schematic configuration diagram of an embodiment of an apparatus for producing a gas barrier thin film coated plastic container by an atmospheric pressure plasma CVD method. In FIG. 2, the chamber is a schematic cross-sectional view. The manufacturing apparatus according to the present embodiment has an accommodation space 35 that can accommodate almost the whole of the container excluding the opening of the plastic container 21 or the entire container so that there is a gap enough to generate plasma, and the inner space of the plastic container 21. The chamber 36 also serving as an external electrode for housing and holding the plastic container 21 so that the gas in the housing space 35 does not flow into the chamber, and the electrolysis for filling the plastic container 21 with an electrolytic solution that is detachably disposed inside the plastic container 21. A liquid injection tube 23 and an internal electrode 23 that is detachably disposed in the plastic container 21 so as to come into contact with the electrolyte when the plastic container 21 is filled with the electrolyte (also shown in FIG. 2) And an electromagnetic wave supplying means 27 for supplying electromagnetic power to the internal electrode 23, and plasma generation under atmospheric pressure. The gas barrier thin film and a raw material gas supply means 30 for supplying outside the plastic container 21 of the feed gas accommodating space 35 with an inert gas for forming the outer surface of the plastic container 21. In the case of atmospheric pressure plasma, it is necessary that the distance between the electrodes on the outer surface of the plastic container and the inner wall surface of the chamber is such that a gap is generated so that plasma is generated. If the distance between the electrodes is too wide, the discharge will not be stable. For example, in order to stabilize the discharge, the distance between the electrodes is desirably 5 mm or less, preferably 3 mm or less. In addition, since it is necessary to supply source gas between an external electrode and the PET bottle surface, these are not stuck. In order to form a denser film, it is preferable to perform gas replacement of the atmosphere.

  The chamber 36 has a function equivalent to that of the vacuum chamber 16 except that the chamber 36 does not need to have sufficient strength to withstand vacuum. However, unlike the case of the first embodiment, as shown in FIG. 2, it is necessary to provide a gap between the external electrode and the PET bottle surface so that plasma is generated, for example, a gap of about several millimeters. Accordingly, a similar accommodation space 35 that is slightly larger than the shape of the outer surface of the container is provided. Further, in order to accommodate the plastic container 21 in the similar accommodation space 35, the chamber body 22 is divided into at least two parts at the vertical division line 37, and is composed of chamber main bodies 22a and 22b. Further, as shown in FIG. 3, the chamber bodies 22a and 22b can be opened and closed by the chamber opening and closing means 40, and the plastic container is taken in and out in the open state, and the film formation is performed in the closed state. The chamber body 22 may be divided not only in the above-described vertical division but also in the horizontal division in order to facilitate the setting of the plastic container. The chamber body 22 is supported by an air cylinder 26 so as to be lifted and lowered. On the other hand, for easy setting of the plastic container 21, the lid 33 may be appropriately divided while ensuring hermeticity. In order to replace the atmosphere outside the bottle, the chamber 36 needs a certain level of pressure resistance.

  The electrolyte injection tube 23, the electrolyte supply means 31, the internal electrode 23, and their relationship are the same as in the first embodiment.

  In order to generate plasma at atmospheric pressure, the electromagnetic wave supply means 27 preferably sets the frequency of the applied electrode to 2 kHz to 1000 kHz so as to enable stable glow discharge at atmospheric pressure. In this embodiment, the frequency is different from that of the high-frequency supply means of the first embodiment for the purpose of generating plasma at atmospheric pressure, but there are overlapping frequency bands.

  The nozzle seal 25 and the source gas supply means 30 are the same as those in the first embodiment. The exhaust means 28 is installed not for the purpose of evacuating the accommodation space 35 of the chamber 36 but for quickly supplying the source gas. The exhaust means 28 is formed by a vacuum valve (not shown), an exhaust pump (not shown), and piping connecting them. The exhaust means 29 is for adjusting the differential pressure between the electrolyte injection pressure and the container internal pressure.

  The resin type of the plastic container, the type of raw material gas, the combination thereof, and the electrolytic solution are the same as those in the first embodiment.

  In the second embodiment, the electromagnetic wave supply means 27 supplies high-frequency power to the internal electrode 23 as shown in FIG. However, the electromagnetic wave supply means 27 may be configured to supply high-frequency power to an external electrode that also serves as the vacuum chamber 36. In FIG. 5, the form which connected the electromagnetic wave supply means 27 to the chamber main body 22 which is a conductor was shown. In this case, it is considered that a potential difference is generated between the storage space 35 and the outer surface of the container which is the ground potential, and the plasma source gas is attracted to the outer surface of the container due to this potential difference, and gas barrier properties are formed on the outer surface of the container. A thin film is formed.

  In the first embodiment and the second embodiment, the volume of the internal electrode in the portion immersed in the electrolytic solution, the volume of the electrolytic solution injection tube, or the volume of the internal electrode that also serves as the electrolytic solution injection tube is below the neck ring. It is preferable that the volume is substantially the same as the head space. That is, in this embodiment, since the electrolyte is a conductive medium for plasma excitation power, when the plasma is generated, the electrolyte level is raised to the neck ring, so that a uniform thin film from the bottom of the container to the neck ring height is formed. A film can be formed. In order to adjust the rise in the liquid level, the volume of the internal electrode immersed in the electrolytic solution or the electrolytic solution injection tube is set to be substantially the same as the head space under the neck ring. The head space is the volume of the unfilled space from the liquid level to the lid when the container is filled with a beverage.

(Film Forming Method in First Embodiment)
Next, a procedure for forming a gas barrier thin film on the outer surface of a plastic container using the manufacturing apparatus of this embodiment will be described with reference to FIG. Here, a case where a DLC film is formed as a gas barrier thin film will be taken as an example. For example, a PET bottle is used as the plastic container 1. When the manufacturing apparatus shown in FIG. 4 is used, the gas barrier thin film can be formed on the outer surface of the plastic container by the same procedure, although the supply destination of the high frequency power is different from that in FIG.

  First, the vent (not shown) is opened to open the accommodation space 15 to the atmosphere. Next, the chamber body 2 is removed from the lid 13. Next, the PET bottle 1 is fitted into the opening provided in the lid 13 in the vicinity of the neck ring 14 with good airtightness, and the PET bottle 1 is held by the lid 13. Then, the air cylinder 6 is raised and the chamber body 2 is brought into contact with the lid 13 with good airtightness so as to be evacuated. At this time, the PET bottle 1 is accommodated in the accommodating space 15, and the gas in the accommodating space 15 is prevented from flowing into the inner space of the plastic container. At this time, the internal electrode 3 also serving as an electrolyte solution injection tube is inserted into the PET bottle 1 through the mouth opening of the PET bottle 1 and placed in the container. The top surface of the container mouth is in contact with the nozzle seal 5 so as to be airtight, and is sealed by the exhaust means 9 so as to be evacuated.

  Next, an electrolytic solution, for example, an ionic sports drink is filled into the PET bottle 1 through the electrolytic solution injection tube 3. Filling is performed while adjusting the differential pressure between the injection pressure of the beverage and the pressure in the container by the exhaust means 9 so that the beverage does not foam. Then, the electrolytic solution is injected so that the liquid level comes near the neck (neck ring) of the PET bottle. At this time, the internal electrode 3 disposed inside the PET bottle 1 is disposed in contact with the electrolytic solution. In FIG. 1, the internal electrode 3 (also serving as an electrolyte injection tube) is inserted into the electrolyte, but may be in contact with the liquid surface.

  Next, after closing the vent, the vacuum means 8 is operated to exhaust the air outside the PET bottle 1 in the accommodation space 15 to form a decompression space. The decompression space is decompressed until it reaches a required degree of vacuum, for example, 5 Pa to 15 Pa or less. This is because if the degree of vacuum exceeding the degree of vacuum is sufficient, the storage space 15 has too many impurities. Thereafter, the raw material gas (for example, acetylene) sent from the raw material gas supply means 10 with the flow rate controlled is introduced into the decompression space from the outlet provided in the lid 13. The supply amount of this raw material gas is preferably 20 to 50 ml / min.

  Note that the inner space of the PET bottle is depressurized to adjust the differential pressure when the electrolyte solution is filled. At this time, the vacuum means 8 is activated to prevent the container from being crushed. The outside of the plastic container 1 may be decompressed simultaneously.

  After the concentration of the raw material gas becomes constant and stabilized at a predetermined film forming pressure, for example, 7 to 22 Pa, by the balance between the controlled gas flow rate and the exhaust capability, the high frequency power is supplied to the internal electrode 3 by operating the high frequency supply means 7. Apply. At this time, the electrolytic solution in contact with the internal electrode 3 is ionized to become a high-frequency power conducting medium, and the high-frequency power is conducted to the PET bottle which is an insulator. As a result, electrons accumulate on the wall surface of the container, a predetermined potential drop occurs, and a negative self-bias voltage is applied to the outer surface of the PET bottle. At this time, since the container and the electrolytic solution are in contact with each other, a uniform and sufficient self-bias voltage can be applied to the outer surface of the container. At this time, source gas plasma is generated in the decompression space. At this time, hydrocarbon carbon and hydrogen, which are source gases present in the plasma, are each ionized positively. Then, the ions collide randomly with the outer surface of the PET bottle 1. Due to such a sputtering effect, bonding between adjacent carbon atoms, bonding between carbon atoms and hydrogen atoms, and separation of once bonded hydrogen atoms occur. Thus, an extremely dense DLC thin film is formed on the outer surface of the PET bottle 1 by the low pressure plasma CVD method. In addition, the output (for example, 13.56 MHz) of the high frequency supply means 7 is approximately 200 to 500 W. In addition, plasma discharge is sustained in a reduced pressure space by applying an appropriate high frequency output. The film formation time is as short as several seconds. In the present invention, since a uniform and sufficient self-bias voltage can be applied in this way, the thin film can be formed so as to have a good adhesion and function as a gas barrier thin film.

  Next, the RF output from the high-frequency supply means 7 is stopped, and further, the supply of the raw material gas is stopped. Thereafter, the hydrocarbon gas in the decompressed space where the plasma is generated is exhausted by the vacuum means 8. Thereafter, the vacuum valve (not shown) arranged in the path of the vacuum means 8 is closed, and the exhaust pump (not shown) is stopped. Thereafter, the vent (not shown) is opened to open the decompression space to the atmosphere, and the PET bottle 1 filled with the electrolytic solution is taken out from the storage space 15. Then, by repeating the film forming method described above, a DLC film is formed on the outer surface of the next PET bottle.

When the electrolytic solution is a beverage, gassing or the like is performed so as to prevent air (oxygen) from entering the space of the container mouth, that is, the head space, from the surface of the beverage. PET bottles filled with beverages are shipped with product labels attached as necessary.

(Film Forming Method in Second Embodiment)
Next, a procedure for forming a gas barrier thin film on the outer surface of a plastic container by the atmospheric pressure plasma CVD method using the manufacturing apparatus of this embodiment will be described with reference to FIG. A case where a DLC film is formed as a gas barrier thin film will be taken as an example. For example, a PET bottle is used as the plastic container 23. When the manufacturing apparatus shown in FIG. 5 is used, the gas barrier thin film can be formed on the outer surface of the plastic container by the same procedure, although the supply destination of the high frequency power is different from that in FIG.

  The chamber body 22 has a left and right divided structure, and is 22a and 22b, respectively. In the case of normal pressure, the inter-electrode distance between the outer surface of the plastic container and the inner wall surface of the chamber needs to have a gap enough to generate plasma. For example, in order to stabilize the discharge, the distance between the electrodes is 0.5 to 5 mm, preferably 1 to 3 mm. In this embodiment, the distance is set to 2.5 mm. First, the accommodation space 15 is open to the atmosphere. The chamber body 22 is removed from the lid 33. Next, the chamber body 22 is opened by the chamber opening / closing means 40, the plastic container 21 is set in the accommodation space 35, and the chamber body 22 is closed by the chamber opening / closing means 40. At this time, the PET bottle 21 is fitted into the opening provided in the lid 33 in the vicinity of the neck ring 34, and the PET bottle 21 is held by the lid 33. Further, in order to prevent leakage of an ignitable source gas such as acetylene, the PET bottle 21 is fitted into the lid 33 with good airtightness, and further set in contact with the lid 33 with good airtightness. At this time, it is preferable that the chamber 36 be sealed to prevent leakage of the raw material gas. At this time, the PET bottle 21 is stored in the storage space 35 and sealed so that the gas in the storage space 35 does not flow into the internal space of the plastic container. At this time, the internal electrode 23 that also serves as an electrolyte solution injection tube is inserted into the PET bottle 21 through the mouth opening of the PET bottle 21 and disposed in the container. The top surface of the container mouth is in contact with the nozzle seal 25 so as to have airtightness, and is sealed by the exhaust means 28 so as to be evacuated.

  Next, as in the case of the first embodiment, an electrolytic solution, for example, an ionic sports drink, is filled in the PET bottle 21 so as not to be foamed while the exhaust means 29 is operated. Before filling, the inside of the container is replaced with nitrogen gas or carbon dioxide gas, and the height of the filling liquid is set up to the neck with the internal electrode 23 inserted.

  Next, the exhaust gas 28 is operated to exhaust the air outside the PET bottle 21 in the accommodation space 35, and the raw material gas (for example, acetylene) sent from the raw material gas supply device 30 with the flow rate controlled is an inert gas. Along with (for example, argon), the air is introduced into the exhaust space from the air outlet provided in the lid 13. The supply amount of the raw material gas is preferably 5 to 50 L / min. By this operation, the outside of the PET bottle 21 in the accommodation space 35 is replaced with a mixed gas of the source gas and the inert gas.

  After the concentration of the raw material gas becomes constant and stabilized at a predetermined film forming pressure, for example, 10 kPa to atmospheric pressure, by the balance between the controlled gas flow rate and the exhaust corresponding to the flow rate, the internal electrode is operated by operating the electromagnetic wave supply means 27. Electromagnetic wave power is applied to 23. At this time, as in the first embodiment, the electrolyte in contact with the internal electrode 23 is ionized to become a conductive medium for electromagnetic power, and the electromagnetic power is conducted to the PET bottle that is an insulator. As a result, electrons accumulate on the wall surface of the container, a predetermined potential drop occurs, and a negative self-bias voltage is applied to the outer surface of the PET bottle. At this time, since the container and the electrolytic solution are in contact with each other, a uniform and sufficient self-bias voltage can be applied to the outer surface of the container. At this time, the raw material gas containing the inert gas is turned into plasma even at 10 kPa to atmospheric pressure. As in the first embodiment, the ions collide randomly on the outer surface of the PET bottle 21 to form a film. In this way, an extremely dense DLC thin film is formed on the outer surface of the PET bottle 21 by the atmospheric pressure plasma CVD method. In addition, the output (for example, 5 kHz) of the electromagnetic wave supply means 27 is approximately 10 kW to 50 kW. Further, plasma discharge is sustained even at atmospheric pressure by applying an appropriate electromagnetic wave output. The film formation time is as short as several seconds. Also in this embodiment, since it is possible to apply a uniform and sufficient self-bias voltage in this way, the thin film can be formed to have good adhesion and function as a gas barrier thin film.

  Next, the output from the electromagnetic wave supply means 27 is stopped, and further, the supply of the raw material gas and the inert gas is stopped. Thereafter, the hydrocarbon gas in the space where the plasma is generated is exhausted by the exhaust means 28. Thereafter, the PET bottle 21 filled with the electrolytic solution is taken out from the accommodation space 35. Then, by repeating the film forming method described above, a DLC film is formed on the outer surface of the next PET bottle.

Next, when the electrolytic solution is a beverage, it is plugged in the same manner as in the first embodiment, and shipped with a product label attached as necessary.

  In the first and second embodiments, the DLC film is formed to have a thickness of 10 to 50 nm.

(Example corresponding to the first embodiment (low pressure CVD method); Example 1)
The plastic container used in this example has a capacity of 500 ml, a container height of 200 mm, a container body diameter of 71.5 mm, a mouth opening inner diameter of 21.74 mm, an outer diameter of 24.94 mm, and a container body thickness of 0.3 mm. PET container having a resin amount of 32 g / polyethylene terephthalate resin (PET resin RT553 manufactured by Nihon Unipet Co., Ltd.).

The evaluation method of the DLC film is as follows. The oxygen permeability of this container is Moden
Measurement was performed under the conditions of 23 ° C. and 90% RH using an Oxtran 2/20 manufactured by Control, and the measured value 72 hours after the start of nitrogen gas replacement was described. The film thickness of DLC was measured using Veeco DEKTAK3.

  The oxygen permeability before coating of the plastic container used in this example was 0.0330 ml / container (500 ml PET container) / day) (23 ° C. RH 90%, measured value 72 hours after the start of nitrogen gas replacement). It was.

  The apparatus used in this embodiment is the apparatus shown in FIG. In this example, the DLC film was formed according to the first embodiment. When filling an ionic sports drink as an electrolytic solution, the ionic sports drink is injected so that the liquid level is near the neck of the PET bottle. At this time, unless otherwise specified, a high-frequency power output (13.56 MHz) of 400 W, a flow rate of acetylene as a raw material gas of 40 ml / min, and a film forming time of 2 seconds were used. The film thickness of the DLC film was approximately 30 nm (average of the entire container). In this embodiment, since a uniform and sufficient self-bias voltage can be applied, the thin film can be formed so as to have good adhesion and function as a gas barrier thin film.

  The PET bottle thus produced had the oxygen permeability shown below. When a DLC film was formed to a thickness of 30 nm (average over the entire container), the oxygen permeability was 0.0040 ml / container (500 ml PET container) / day) (measured value at 23 ° C. RH 90%, 72 hours after the start of nitrogen gas replacement) Met. Compared to the uncoated container, the gas barrier property was improved about 8 times.

(Example corresponding to the second embodiment (atmospheric pressure CVD method); Example 2)
The same PET bottle used in Example 1 was used in this example, and the same evaluation was performed. The apparatus shown in FIG. 2 was used. The film forming method followed the film forming method according to the second embodiment. When filling an ionic sports drink as an electrolytic solution, the ionic sports drink is injected so that the liquid level is near the neck of the PET bottle. Unless otherwise specified, the high-frequency power output (5 kHz) was 30 kW, the raw material gas flow rate was 15 L / min, and the film formation time was 3 seconds. The film thickness of the DLC film was approximately 10 to 50 nm (average of the entire container). Also in Example 2, since it was possible to apply a uniform and sufficient self-bias voltage, the thin film could be formed to have good adhesion and function as a gas barrier thin film.

  The PET bottle thus produced had the oxygen permeability shown below. When the DLC film was formed to a thickness of 30 nm (average for the entire container), the oxygen permeability was 0.0050 ml / container (500 ml PET container) / day) (measured value after 23 hours at RH 90%, nitrogen gas replacement 72 hours) Met. Compared to the uncoated container, the gas barrier property was improved about 7 times.

It is a schematic block diagram of one form of the manufacturing apparatus of the gas barrier property thin film coating plastic container by a low pressure plasma CVD method. It is a schematic block diagram of one form of the manufacturing apparatus of the gas barrier thin film coating plastic container by a normal pressure plasma CVD method. It is the conceptual diagram which looked at the chamber of the apparatus of FIG. 2 from the upper part, Comprising: It is a figure which shows the open / close state of a chamber. It is a schematic block diagram of another form of the manufacturing apparatus of the gas barrier thin film coating plastic container by low pressure plasma CVD method. It is a schematic block diagram of another form of the manufacturing apparatus of the gas barrier thin film coating plastic container by an atmospheric pressure plasma CVD method.

Explanation of symbols

1,21, plastic container
2,22, chamber body
3,23, Electrolyte injection tube (also used as internal electrode)
4,24, O-ring
5,25, Nozzle seal
6,26, Air cylinder
7, high frequency supply means
8, vacuum means
9,28,29, exhaust means
10,30, Material gas supply means
11,31, electrolyte supply means
12,32, electrolyte
13,33, lid
14,34, neck ring
15,35, containment space
16, vacuum chamber
27, Electromagnetic wave supply means
36, chamber
37, vertical dividing line
40, chamber opening / closing means

Claims (12)

  An external electrode for accommodating and holding the plastic container so that the gas in the storage space does not flow into the internal space of the plastic container, the housing having a storage space capable of accommodating almost the entire container except the mouth of the plastic container or the entire container; A vacuum chamber that also serves as an electrolyte, an electrolyte injection tube that is detachably disposed inside the plastic container and that fills the plastic container with the electrolyte, and contacts the electrolyte when the plastic container is filled with the electrolyte An internal electrode detachably disposed in the plastic container, high-frequency supply means for supplying high-frequency power to the internal electrode or the external electrode, and decompressing the outside of the plastic container in the housing space And a raw material gas for forming a gas barrier thin film on the outer surface of the plastic container by converting it into a plasma. Apparatus for manufacturing a gas barrier thin film coating container, characterized in that it comprises a source gas supply means for supplying to the outside of the plastic container of the volume space.   There is a housing space that can be accommodated so that there is a gap enough to generate plasma over the entire container or the entire container except the mouth of the plastic container so that the gas in the housing space does not flow into the inner space of the plastic container. A chamber also serving as an external electrode for accommodating and holding the plastic container, an electrolyte injection pipe that is detachably disposed in the plastic container and fills the plastic container with an electrolyte, and an electrolyte in the plastic container An internal electrode detachably disposed inside the plastic container so as to come into contact with the electrolytic solution when filled, electromagnetic wave supply means for supplying electromagnetic power to the internal electrode or the external electrode, and atmospheric pressure The raw material gas for forming a gas barrier thin film on the outer surface of the plastic container under plasma is formed together with the inert gas. Apparatus for manufacturing a gas barrier thin film coating container, characterized in that it comprises a source gas supply means for supplying to the outside of the plastic container of the volume space.   The apparatus for manufacturing a gas barrier thin film coating container according to claim 1 or 2, wherein the internal electrode has a tubular shape and is also used as the electrolyte solution injection pipe.   A nozzle seal that penetrates the internal electrode and seals the mouth of the plastic container is provided, and when the plastic container is held in the vacuum chamber or the chamber, airtightness is obtained in the neck ring of the plastic container. The apparatus for producing a gas barrier thin film coating container according to claim 1, 2 or 3, wherein the container is sealed.   The electrolyte solution serves as a liquid to be filled in a plastic container, and becomes a plasma excitation power conduction medium when plasma excitation power is applied to the internal electrode or the external electrode. The apparatus for producing a gas barrier thin film coating container according to 2, 3 or 4.   6. The gas barrier thin film coating container according to claim 1, wherein the electrolytic solution is one of beer, wine, fruit juice beverage, tea-based beverage, carbonated beverage or sports beverage. Manufacturing equipment.   The source gas is a gas containing a carbon compound as a main component, a gas containing an organosilicon compound as a main component, or a gas containing a mixed gas of a carbon compound and an organosilicon compound as a main component. The apparatus for manufacturing a gas barrier thin film coating container according to claim 1, 2, 3, 4, 5 or 6.   The volume of the internal electrode in the portion immersed in the electrolytic solution or the volume of the electrolytic solution injection tube or the volume of the internal electrode also serving as the electrolytic solution injection tube according to claim 3 is substantially equal to a head space under the neck ring. 8. The apparatus for producing a gas barrier thin film coating container according to claim 1, wherein the volume is the same.   The entire plastic container except the mouth of the plastic container or the entire container is accommodated and held in a vacuum chamber also serving as an external electrode so that gas does not flow from the inside of the vacuum chamber into the inner space of the plastic container. And an internal electrode is disposed in the plastic container so as to be in contact with the electrolytic solution, and a gas barrier thin film is formed in the decompression space with the outside of the plastic container as a decompression space in the vacuum chamber. A gas barrier property characterized in that, after supplying a raw material gas, high-frequency power is applied to the internal electrode or the external electrode to turn the raw material gas into a plasma to form a gas barrier thin film on the outer surface of the plastic container. Manufacturing method of thin film coated plastic container.   Before filling the plastic container with the electrolytic solution, the plastic container is evacuated, and carbon dioxide or nitrogen gas is supplied to replace the gas to remove residual oxygen in the plastic container, and 10. The gas barrier thin film-coated plastic container according to claim 9, wherein the outside of the plastic container in the vacuum chamber is in a reduced pressure state so that the plastic container is not crushed when the plastic container is evacuated. Production method.   A chamber that also serves as an external electrode, except for the opening of the plastic container, or the entire container has a clearance enough to generate plasma and accommodates the gas so that no gas flows from the chamber into the inner space of the plastic container. An internal electrode is disposed inside the plastic container so that the plastic container is filled with an electrolytic solution and in contact with the electrolytic solution, and a gas barrier thin film source gas is disposed outside the plastic container in the chamber. A gas barrier thin film is formed on the outer surface of the plastic container by supplying electromagnetic power to the internal electrode or the external electrode to make the source gas into plasma under atmospheric pressure. A method for producing a gas-barrier thin film-coated plastic container. 12. The method of manufacturing a gas barrier thin film-coated plastic container according to claim 11, wherein after supplying and replacing the raw material gas of the gas barrier thin film together with an inert gas outside the plastic container in the chamber, the internal electrode or the 12. The gas barrier thin film-coated plastic according to claim 11, wherein an electromagnetic wave power is applied to an external electrode so that the raw material gas is converted into plasma under atmospheric pressure to form a gas barrier thin film on the outer surface of the plastic container. Container manufacturing method.

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