Film deposition device, film deposition method, container manufacturing method, and container

Abstract

To provide a film deposition device for restraining thermal alteration of a container.SOLUTION: A film deposition device 1 for depositing a barrier film 5A on an inner face of a container 5 by a plasma system comprises: a vacuum chamber 10 partitioned to a first space R1 and a second space R2, in which the container is arranged; an anode electrode 21 arranged in the first space R1 on a side of the second space R2; a cathode electrode 22 arranged in the first space R1 opposite to the anode electrode 21; a raw material gas supply mechanism 30 for supplying raw material gas of the barrier film 5A to the first space R1; and an exhaust mechanism 40 for exhausting air from the second space R2. The anode electrode 21 functions as a partition member of the first space R1 and the second space R2 in the vacuum chamber 10, has a hole 21A through which the first space R1 communicates with the second space R2, and has a tubular member 21B communicating with the hole 21A and extending to the second space R2, so as to extend to inside of the container 5.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a film forming apparatus for forming a barrier film on the inner surface of a container, a film forming method using the film forming apparatus, a container manufacturing method using the film forming method, and a container having a barrier film formed on its inner surface. [Background technology]

[0002] There is known a film forming technique for forming a barrier film on the inner surface of a container in order to protect contents contained in the container from the environment outside the container such as moisture, gas, or light, or to protect the container from contents contained in the container such as liquid, gas, etc. For example, Patent Document 1 discloses a film forming apparatus for forming a barrier film on the inner surface of a container.

[0003] The film forming apparatus disclosed in Patent Document 1 includes a first electrode (anode electrode) that surrounds the outside of a container, and a second electrode (cathode electrode) that is inserted inside the container and also serves as a supply pipe for raw material gas for the barrier film, and generates plasma inside the container to form a barrier film inside the container. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-8669 Summary of the Invention [Problem to be solved by the invention]

[0005] In the film forming apparatus disclosed in Patent Document 1, since plasma is generated inside a container, it is conceivable that electrons in the plasma collide with the container, causing the container to heat up. Therefore, if the container is made of a material that is weak against heat, it is conceivable that the container may be thermally altered.

[0006] An object of the present invention is to provide a film forming apparatus, a film forming method, a container manufacturing method, and a container that suppress thermal deterioration of the container. [Means for solving the problem]

[0007] The film forming apparatus according to the present invention is a film forming apparatus for forming a barrier film on the inner surface of a container by a plasma method, and includes a vacuum chamber partitioned into a first space and a second space in which the container is placed, an anode electrode arranged on the second space side of the first space, a cathode electrode arranged in the first space so as to face the anode electrode, a source gas supply mechanism for supplying a source gas of the barrier film to the first space, and an exhaust mechanism for exhausting the second space. The anode electrode functions as a partition member between the first space and the second space in the vacuum chamber, has a hole communicating between the first space and the second space, and has a tubular member communicating with the hole and extending to the second space side so as to extend into the inside of the container.

[0008] The film forming method of the present invention is a film forming method for forming a barrier film on the inner surface of a container using the above-mentioned film forming apparatus, comprising the steps of: (1) evacuating the second space of the vacuum chamber by the exhaust mechanism, and evacuating the first space of the vacuum chamber through the hole in the anode electrode and the tubular member; (2) supplying a raw material gas for the barrier film to the first space of the vacuum chamber by the raw material gas supply mechanism; (3) generating plasma in the first space by the anode electrode and the cathode electrode to generate active species of the raw material gas; (4) evacuating the second space by exhausting with the exhaust mechanism, and drawing the active species of the raw material gas generated in the first space into the container through the hole in the anode electrode and the tubular member, thereby forming the barrier film inside the container; and (5) electrons in the plasma head toward the anode electrode without colliding with the container.

[0009] The method for producing a container according to the present invention uses the above-mentioned film forming method to produce a container having a barrier film formed on its inner surface.

[0010] The container according to the present invention is a container having a barrier film formed on its inner surface using the above-mentioned film forming apparatus. Effect of the Invention

[0011] According to the present invention, even if the container is made of a material that is sensitive to heat, a barrier film can be formed on the inner surface of the container while suppressing thermal deterioration of the container. [Brief description of the drawings]

[0012] [Figure 1] FIG. 2 is a schematic diagram showing a film forming apparatus and a container according to the present embodiment. [Diagram 2] 2 is a perspective view showing an anode electrode in the film forming apparatus shown in FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings. In each drawing, the same or corresponding parts are denoted by the same reference numerals. For convenience, hatching and reference numerals may be omitted, in which case other drawings shall be referred to.

[0014] (film forming equipment) Fig. 1 is a schematic diagram showing a film forming apparatus and a container according to this embodiment, and Fig. 2 is a perspective view showing an anode electrode in the film forming apparatus shown in Fig. 1. The film forming apparatus 1 shown in Fig. 1 is an apparatus that forms a barrier film 5A on the inner surface of a container 5 by a plasma method such as capacitively coupled plasma CVD (Chemical Vapor Deposition). The film forming apparatus 1 includes a vacuum chamber 10, an anode electrode 21, a cathode electrode 22, a raw material gas supply mechanism 30, and an exhaust mechanism 40.

[0015] The vacuum chamber 10 is a chamber that provides a vacuum environment for performing film formation on the container 5. The vacuum chamber 10 is divided into a first space R1 for generating plasma and a second space R2 in which the container 5 is placed and a barrier film 5A is formed on the inner surface of the container 5. A stand (stage) 11 for the container 5 is provided in the second space R2. The stand 11 is movable, for example, in the vertical direction, in order to set the container 5 so that a tubular member (nozzle) 21B of an anode electrode 21, which will be described later, is placed inside the container 5. The vacuum chamber 10 is made of a metal material and may be connected to, for example, a ground potential.

[0016] The anode electrode 21 and the cathode electrode 22 are disposed in the first space R1 of the vacuum chamber 10. Specifically, the anode electrode 21 and the cathode electrode 22 are flat plate-shaped electrodes disposed opposite each other. The anode electrode 21 is disposed on the second space R2 side of the first space R1, and functions as a partition member between the first space R1 and the second space R2 in the vacuum chamber 10.

[0017] The anode electrode 21 is connected to, for example, a ground potential. On the other hand, the cathode electrode 22 is connected to, for example, a power source 7, and, for example, AC power is supplied to the cathode electrode 22. When AC power is supplied to the cathode electrode 22, plasma is generated in the first space R1, and activated species of the source gas are generated.

[0018] The anode electrode 21 has a plurality of holes 21A that communicate between the first space R1 and the second space R2. The anode electrode 21 also has a plurality of tubular members (nozzles) 21B that communicate with each of the holes 21A and extend toward the second space R2 so as to extend into the interior of the container 5. Each of the tubular members 21B is shaped like a funnel having a portion 21C that gradually becomes smaller from the first space R1 side toward the second space R2 side.

[0019] The source gas supply mechanism 30 supplies the source gas for the barrier film 5A to the first space R1 of the vacuum chamber .

[0020] The exhaust mechanism 40 is connected to a vacuum pump (not shown) and evacuates the second space R2 of the vacuum chamber 10. As a result, the active species of the source gas generated in the first space R1 are drawn into the container 5 through the hole 21A of the anode electrode 21 and the tubular members 21B and 12C, and a barrier film 5A is formed on the inner surface of the container 5.

[0021] The film forming apparatus 1 may or may not form a film on the outer surface of the container 5. When a film is not formed on the outer surface of the container 5, for example, the outer surface of the container 5 may be masked.

[0022] (Method of producing film and method of producing container) Next, a film forming method and a container manufacturing method according to the present embodiment will be described.

[0023] First, the second space R2 of the vacuum chamber 10 is evacuated by the exhaust mechanism 40, and then the first space R1 of the vacuum chamber 10 is evacuated through the hole 21A of the anode electrode 21 and the tubular members 21B and 21C. In addition, the raw material gas supply mechanism 30 supplies raw material gas for the barrier film 5A to the first space R1 of the vacuum chamber 10.

[0024] Next, for example, AC power is supplied to the cathode electrode 22. This causes the anode electrode 21 and the cathode electrode 22 to generate plasma in the first space R1 of the vacuum chamber 10, thereby generating activated species of the source gas.

[0025] At this time, the second space R2 of the vacuum chamber 10 is evacuated by the exhaust mechanism 40, and the activated species of the source gas generated in the first space R1 are drawn into the container 5 through the hole 21A of the anode electrode 21 and the tubular members 21B and 21C. As a result, a barrier film 5A is formed inside the container 5.

[0026] At this time, electrons in the plasma move toward the anode electrode 21 having the ground potential without colliding with the vessel 5 or with the collision being suppressed. Also, the electrons in the plasma are attracted to the wall surface of the vacuum chamber 10 having the ground potential.

[0027] Here, the film forming apparatus disclosed in Patent Document 1 includes a first electrode (anode electrode) surrounding the outside of the container, and a second electrode (cathode electrode) inserted into the container and serving as a supply pipe for the raw material gas of the barrier film, and generates plasma inside the container. Therefore, it is considered that electrons in the plasma, that is, electrons that contribute to turning the raw material gas into plasma, collide with the container, causing the container to heat up. Therefore, if the container is made of a material that is weak against heat, it is considered that the container will be thermally altered.

[0028] In this regard, according to the film forming apparatus 1, the film forming method, and the container manufacturing method of this embodiment, the vacuum chamber 10 is divided into the first space R1 and the second space R2, so that plasma is generated in the first space R1, which is different from the second space R2 in which the container 5 is disposed, and active species of the raw material gas are generated. In addition, the anode electrode 21, which functions as a partition member between the first space R1 and the second space R2, has a hole 21A and a tubular member 21B, and the tubular member 21B extends to the inside of the container 5. Therefore, the second space R2 of the vacuum chamber 10 is exhausted by the exhaust mechanism 40, and the anode electrode 21 draws the active species of the raw material gas generated in the first space R1 into the inside of the container 5 through the hole 21A and the tubular member 21B. As a result, a barrier film 5A is formed inside the container 5 by the active species of the raw material gas drawn in.

[0029] On the other hand, since no plasma is generated inside the container 5, it is possible to prevent electrons in the plasma, i.e., electrons that contribute to turning the raw material gas into plasma, from colliding with the container 5. Specifically, in the first space R1 different from the second space R2 in which the container 5 is disposed, the electrons in the plasma are attracted to the anode electrode 21 or the wall surface of the vacuum chamber 10, and are prevented from colliding with the container 5. This prevents the container 5 from generating heat, and prevents thermal deterioration of the container 5 even if the container is made of a material that is weak against heat.

[0030] Thus, according to the film forming apparatus 1, film forming method, and container manufacturing method of this embodiment, a barrier film 5A can be formed on the inner surface of a container 5 while suppressing thermal deterioration of the container, even if the container is made of a heat-sensitive material.

[0031] In other words, the anode electrode 21 is disposed between the cathode electrode 22 and the container 5, and the raw material gas is supplied between the cathode electrode 22 and the anode electrode 21 by the raw material gas supply mechanism 30, and exhausted from the container 5 side by the exhaust mechanism 40. As a result, plasma is generated between the cathode electrode 22 and the anode electrode 21, and active species are generated from the raw material gas. The anode electrode 21 also has a plurality of holes 21A and a plurality of tubular members 21B (nozzles) for circulating the active species inside the container 5. As a result, it is possible to selectively supply the active species into the interior of the plurality of containers 5 while shielding the electrons in the plasma, and it is possible to simultaneously form a barrier film 5A on the inner surface of the plurality of containers 5.

[0032] The tubular member 21B may have a shape such as a rectangle, a semicircle, or an inverted triangle, but is preferably a funnel shape (inverted triangle) having a portion 21C that gradually becomes smaller from the first space R1 side toward the second space R2 side. This makes it possible to appropriately and selectively supply active species to the inside of the vessel 5 while appropriately shielding electrons in the plasma.

[0033] (container) The shape of the container on which the film is to be formed by the film forming apparatus 1 is not particularly limited, and it may be a container that is three-dimensionally shaped and can contain a content such as liquid or gas inside. Examples of materials for the container include polyethylene terephthalate resin (PET), polyethylene terephthalate copolymer resin (copolymer resin using cyclohexane dimethanol or the like instead of ethylene glycol as the alcohol component of polyester), polybutylene terephthalate resin, polyethylene naphthalate resin, aliphatic polyester resin such as polylactic acid (PLA), polyethylene resin (PE), polypropylene resin (PP), cycloolefin resin such as cycloolefin polymer resin (COP) and cycloolefin copolymer resin (COC), ionomer resin, poly-4-methylpentene-1 resin, polymethyl methacrylate resin, polystyrene resin (PS), ethylene-vinyl alcohol copolymer resin, acrylonitrile resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, polyamideimide resin, polyacetal resin, polycarbonate resin (PC), polysulfone resin, fluorinated ethylene resin, styrene-butadiene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, biodegradable resin, and the like. Among these, the present invention is effective for containers formed from materials that are relatively sensitive to heat, such as polyethylene terephthalate resin (PET), polystyrene resin (PS), polyvinyl chloride resin, and biodegradable resin, and is particularly effective when applied to biodegradable resin.

[0034] (biodegradable resin) The biodegradable resin used in the present invention is not particularly limited as long as it has biodegradability. In this embodiment, "biodegradability" refers to a property that can be decomposed into low molecular weight compounds by microorganisms in nature. Specifically, the presence or absence of biodegradability can be determined based on tests suitable for each environment, such as ISO 14855 (compost) and ISO 14851 (activated sludge) under aerobic conditions, and ISO 14853 (aqueous phase) and ISO 15985 (solid phase) under anaerobic conditions. In addition, the decomposition by microorganisms in seawater can be evaluated by measuring biochemical oxygen demand. The biodegradable resin is preferably one or more selected from the group consisting of polyhydroxyalkanoate, polylactic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, polybutylene succinate terephthalate, polycaprolactone, modified starch, and modified cellulose. In the present production method, the biodegradable resin may be used alone or in combination of two or more kinds.

[0035] (Barrier film) The material of the barrier film formed by the film forming apparatus 1 is not particularly limited, and may be any material that has the ability to protect the contents contained in the container from the environment outside the container, such as moisture, gas, or light, or the ability to protect the container from the contents, such as liquid and gas, contained in the container. Examples of the material of the barrier film include diamond-like carbon (DLC), SiOx, SiOxNy, SiNx, SiOxCy, SiOxNyCz, Si-containing diamond carbon, alumina, etc. x, y, and z indicate the composition ratio of each element and are not particularly limited. x and y indicate the composition ratio of each element and are not particularly limited.

[0036] Although the embodiment of the present invention has been described above, the present invention is not limited to the above-mentioned embodiment, and various changes and modifications are possible. In the above-mentioned embodiment, a film forming apparatus 1 is illustrated that includes an anode electrode 21 having a plurality of holes 21A and a plurality of tubular members 21B, 21C and simultaneously forms a barrier film 5A on the inner surface of a plurality of containers 5. However, the present invention is not limited to this, and can also be applied to a film forming apparatus that includes an anode electrode having at least one hole and at least one tubular member and forms a barrier film 5A on the inner surface of at least one container 5. [Explanation of symbols]

[0037] 1 Film forming equipment 5 containers 5A Barrier Film 7 Power 10 Vacuum chamber 11 Platform (stage) 21 Anode electrode 21A hole 21B Tubular member 21C Part of a tubular member 22 Cathode electrode 30 Raw gas supply mechanism 40 Exhaust system R1 First space R2 2nd space

Claims

1. A film forming apparatus for forming a barrier film on the inner surface of a container by a plasma method, a vacuum chamber divided into a first space and a second space in which the container is disposed; an anode electrode disposed on the second space side of the first space; a cathode electrode disposed in the first space so as to face the anode electrode; a source gas supply mechanism for supplying a source gas for the barrier film to the first space; an exhaust mechanism for exhausting the second space; Equipped with The anode electrode is In the vacuum chamber, the insulating member functions as a partition member between the first space and the second space, a hole that communicates the first space with the second space; a tubular member communicating with the hole and extending to the second space side so as to extend into the inside of the container; Film forming equipment.

2. The film forming apparatus according to claim 1 , wherein the tubular member of the anode electrode has a funnel shape having a portion that gradually becomes smaller from the first space side toward the second space side.

3. The film forming apparatus according to claim 1 , wherein the anode electrode is connected to a ground potential.

4. 4. The film forming apparatus according to claim 1, wherein the anode electrode has a plurality of the holes and a plurality of the tubular members corresponding to the plurality of holes, respectively.

5. A film forming method for forming a barrier film on an inner surface of a container using the film forming apparatus according to any one of claims 1 to 3, comprising the steps of: the second space of the vacuum chamber is evacuated by the exhaust mechanism, and the first space of the vacuum chamber is evacuated through the hole of the anode electrode and the tubular member; supplying a source gas for the barrier film to the first space of the vacuum chamber by the source gas supply mechanism; generating plasma in the first space by the anode electrode and the cathode electrode to generate activated species of the source gas; the second space is evacuated by the exhaust mechanism, and the activated species of the source gas generated in the first space are drawn into the container through the hole of the anode electrode and the tubular member, thereby forming the barrier film inside the container; Electrons in the plasma travel toward the anode electrode without colliding with the vessel. Film forming method.

6. A method for manufacturing a container, comprising the steps of: manufacturing a container having a barrier film formed on its inner surface, using the film forming method according to claim 5 .

7. The method for manufacturing a container according to claim 6 , wherein the container comprises a biodegradable resin.

8. The method for manufacturing a container according to claim 7 , wherein the biodegradable resin comprises a polyhydroxyalkanoate resin.

9. A container having a barrier film formed on its inner surface by using the film forming apparatus according to any one of claims 1 to 3.

10. The container according to claim 9, which is made of a biodegradable resin.

11. 11. The container according to claim 10, which is made of a polyhydroxyalkanoate resin.

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