JP2008127053A - Manufacturing method for plastic container coated with oxide film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low cost manufacturing method for a plastic container coated with a gas barrier thin film, whereby a low cost material can be used, a gas barrier thin film can be formed safely at a high speed and executed by using a manufacturing device that requires no expensive equipment and material. <P>SOLUTION: The manufacturing method includes the step in which the inside of a vacuum chamber 6 storing the plastic container 11 is set to a predetermined pressure equal to or below atmospheric pressure, the step in which power is supplied to the wire 18 disposed in the vacuum chamber and heated to a predetermined temperature or above, thereby making the wire hot, and the step in which ozone gas and a non-spontaneous combustible material containing a silicon or metallic element, supplied into the vacuum chamber, are heated by the hot wire, then it is brought into contact with the internal or external surface of the plastic container, thereby forming an oxide thin film from the non-spontaneous combustion material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is suitable for containing, for example, an alcoholic beverage such as beer or the like, which does not oxidize from the quality aspect and requires no escape of carbon dioxide from the container wall, or a soft drink which similarly dislikes oxidation. The present invention also relates to a plastic container for beverages having oxygen gas and carbon dioxide gas barrier properties. More specifically, as an oxygen gas and carbon dioxide gas barrier layer, at least one of the outer and inner surfaces is coated with an oxide thin film that can be deposited safely and at low cost in the food and beverage fields, and is lightweight and impact resistant. And relates to a method for producing a plastic container excellent in recyclability. In addition to the gas barrier property, the plastic having the above-mentioned advantages for coating an oxide thin film having functionality in terms of color transmission / glossiness, translucency / light-shielding properties, cosmetic properties, and discrimination properties relatively easily and at low cost The present invention relates to a container manufacturing method.

In recent years, DLC (Diamond Like) as a single layer thin film coated on PET bottles.
Carbon) membranes have been put into practical use. This DLC film is a film having an amorphous three-dimensional structure of carbon atoms and hydrogen atoms, and is a hard carbon film that is hard, excellent in insulation, has a high refractive index, and has a very smooth morphology.

  Conventionally, there is an example in which such a DLC film forming technique is applied to a plastic container (see, for example, Patent Document 1). A general DLC film forming apparatus described in Patent Document 1 is as follows. That is, as shown in FIG. 1, a plastic container 5 is housed in an external electrode 2 disposed in a reaction chamber 1 having a carbon source gas introduction port 1A and an exhaust port 1B. Then, after the carbon source gas is introduced from the introduction port 1A, a high frequency is applied between the internal electrode 3 and the external electrode 2 from the high frequency power source 4, and the carbon source gas is excited to generate plasma. A DLC film is formed on the inner surface.

  In addition, there is a technique for forming a silicon oxide thin film (SiOx) in a small plastic container instead of a DLC film (see, for example, Patent Document 2). In Patent Document 2, a silicon oxide thin film is formed by plasma CVD as in Patent Document 1.

  Further, there is a technique for forming a silicon nitride film on the surface of a plastic film by catalytic chemical vapor deposition which is a film forming method other than plasma CVD (see, for example, Patent Document 3). As described in Patent Document 3, when a silicon nitride film is formed, methylsilane, dimethylsilane, or trimethylsilane is used as a source gas (Patent Document 3, Paragraph 0004, Paragraph 0022).

Japanese Patent No. 2788412 Japanese Utility Model Publication No. 5-35660 JP 2004-217966 A (paragraph 0004, paragraph 0022)

  However, since the plasma CVD film forming apparatus uses relatively expensive equipment, it is not always inexpensive and can produce a plastic container having gas barrier properties.

  In the catalytic chemical vapor deposition method, it is not necessary to use expensive equipment such as a high-frequency power source, so the cost of the apparatus itself is less than the cost of the plasma CVD film forming apparatus.

  However, when a silicon oxide thin film is formed by catalytic chemical vapor deposition, for example, according to the study by the present inventor, when methylsilane, dimethylsilane or trimethylsilane is used as a source gas, it is sufficient even in an oxygen atmosphere. An oxidation reaction could not be caused and a silicon oxide thin film adhered on a plastic substrate could not be formed. On the other hand, if silicon hydride such as monosilane, disilane, or trisilane is used as the source gas, the explosiveness and danger represented by pyrophoric properties are high, and the safety device is expensive. Cost merit is diminished. Furthermore, when forming a silicon oxide thin film, it is necessary to supply a source gas and an oxidizing gas together. However, if tungsten wire is used as a thermal catalyst (Patent Document 3, paragraph 0059), tungsten is oxidized. There is a problem of deterioration.

  Further, even though the catalytic chemical vapor deposition method can form a film on a planar object such as a plastic sheet, there is no report that a film can be formed on a three-dimensional object such as a plastic container.

  Here, the present invention is mainly directed to plastic containers for the beverage / food field. In this field, there are significant cost constraints on products related to handling beverages and foods, and the use of safe methods and materials for production processes and product containers. Therefore, the use of pyrophoric raw materials typified by the above silanes and alkylaluminums is not practical from the viewpoints of safety management cost and safety awareness. Such raw materials are, for example, designated as special high-pressure gas and hazardous material type 3 in Japan. For the same reason and consideration for the environment, the use of raw materials containing halogens is generally avoided in this field and is not practical from the viewpoint of the present invention.

  Therefore, the object of the present invention is to make the container having a three-dimensional shape made of plastic at room temperature non-pyrophoric in the method for producing a gas barrier thin film-coated plastic container without relying on these impractical raw materials. To provide a low-cost production method that uses raw materials and ozone, enables safe, high-speed, gas-barrier thin film deposition at low temperatures, and that can be operated on production equipment that does not require expensive equipment. It is.

  In addition, containers in the beverage / food field are required to have translucency / light-shielding properties and coloration to protect the contents, visually check the quality, and improve the appearance. For such problems, practical translucent / light-shielding properties and coloration can be controlled with a high degree of freedom, without being colored directly, and it is inexpensive and highly recyclable. It is also an object of the present invention to provide a manufacturing method applied to the container.

  The present inventor has eagerly developed to solve the above-mentioned problems. After heating the wire with heat and heating a non-pyrophoric raw material with high safety together with ozone gas with this hot wire, the film is deposited on the surface of the plastic container. As a result of contact, it was found that an oxide having a gas barrier property derived from a non-pyrophoric material can be formed with good adhesion, and the present invention was completed.

  Here, in this invention, a wire means the object which can heat an electrical resistor to several hundred degrees or more by electricity supply using a general industrial power supply. Typically, it is a metal wire, but a conductive metal compound or carbon rod-like body / fiber body is also included in this concept. Furthermore, an object having a carrier or a coating on these objects is also included in the concept. In any case, when forming a film on the surface of a plastic container, the resistance heating element is arranged so that the heat load on each part of the container surface and the flow of the film forming material are suitable for film formation, even for complicated three-dimensional shapes. This is because they are in common. Relatedly, in the present invention, a hot wire means a wire that is resistance-heated by energization.

  Specifically, the method for manufacturing a plastic container coated with an oxide thin film according to the present invention includes a step of setting the inside of a vacuum chamber containing the plastic container to a predetermined pressure equal to or lower than atmospheric pressure, and disposing the plastic container inside the vacuum chamber. A process of energizing the wire being heated to generate heat above a predetermined temperature to form a hot wire, and a non-pyrophoric raw material and ozone gas containing silicon or a metal element as a constituent element supplied to the inside of the vacuum chamber, Heating with the hot wire, and then contacting the inner surface or the outer surface of the plastic container to form an oxide thin film derived from the non-pyrophoric raw material. And

  In the method of manufacturing a plastic container coated with an oxide thin film according to the present invention, the plastic container is carried into the vacuum chamber via a differential pressure mechanism, and the plastic container is transported in the vacuum chamber. A step of being transported on the transport path so that the surface of the plastic container approaches a desired distance from the wire installed in the path, and the plastic container is moved out of the vacuum chamber via a differential pressure mechanism. It is preferable to further include a step of unloading. It is also possible to mass-produce plastic containers coated with oxide thin films.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, the distance between the inner surface or outer surface of the plastic container and the hot wire is 5 to 50 mm, and the pressure in the vacuum chamber is 10 to 100 Pa. It is preferable that It is possible to prevent particle formation in the gas phase due to decomposition of the non-pyrophoric raw material and to form an oxide thin film on the surface of the plastic container at high speed.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, it is preferable that the plastic container is irradiated with ultraviolet rays in the step of forming the oxide thin film. The surface of the plastic container can be sterilized. Moreover, the decomposition of ozone can be promoted by irradiation with ultraviolet rays to increase the oxidizing power, and the oxidation of non-pyrophoric raw materials can be promoted. At this time, the non-pyrophoric raw material and the ozone gas are heated by the hot wire, but since the irradiation of ultraviolet rays is not hindered by the hot wire, the reaction can be efficiently advanced.

In the method for producing a plastic container coated with an oxide thin film according to the present invention, a non-pyrophoric silicified organic compound is used as the non-pyrophoric raw material, and the hot wire is decomposed by a thermal decomposition reaction or catalytic reaction. Then, a SiO _x thin film is formed as the oxide thin film, or a non-pyrophoric aluminum-containing organic compound is used as the non-pyrophoric raw material and decomposed by a thermal decomposition reaction or catalytic reaction with the hot wire. Thus, it is preferable to form an AlO _x thin film as the oxide thin film. Unlike non-pyrophoric silicified organic compounds or non-pyrophoric aluminum-containing organic compounds, unlike pyrophoric raw materials such as silane-based materials or trimethylaluminum, safety is not required, As a result, it is inexpensive. Further, even if these non-pyrophoric materials are supplied simultaneously with oxygen and heated with a hot wire, an adherent SiO _x thin film or AlO _x thin film is not formed on the plastic substrate. Only when non-pyrophoric raw materials and ozone gas are simultaneously supplied and heated with a hot wire as in the present invention, thermal decomposition and oxidation are sufficiently advanced to form a SiO _x thin film or an AlO _x thin film with good adhesion to the substrate. Is done.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, the supply amount of the ozone gas is preferably such that carbon remaining in the oxide thin film is substantially zero. If the supply amount of ozone gas is small, carbon remains in the oxide thin film. If the supply amount is sufficient or more, carbon does not remain in the oxide thin film.

  When the carbon remaining in the oxide thin film is substantially zero, the gas barrier property is the best. Here, the fact that carbon is substantially zero means that, in the case of a SiOx thin film as a specific example, the amount of carbon in the oxide thin film is 5 atom% or less.

  In the method for manufacturing a plastic container coated with an oxide thin film according to the present invention, the supply amount of the ozone gas is set to an amount in which carbon remains in the oxide thin film at the start of the formation of the oxide thin film, and then supplied. Increasing the amount to set the amount of carbon remaining in the oxide thin film to substantially zero, and making the oxide thin film a gradient composition thin film having a different carbon content in the thickness direction preferable. If the supply amount of ozone gas is small, carbon remains in the oxide thin film. If the supply amount is sufficient or more, carbon does not remain in the oxide thin film. When carbon remains in the oxide thin film, the adhesion to the substrate becomes strong. On the other hand, when the carbon remaining in the oxide thin film is substantially zero, the gas barrier property is the best. Therefore, by making the gradient composition film so that carbon remains on the oxide thin film on the substrate surface side and carbon does not remain on the surface side of the oxide thin film, it has excellent adhesion to the substrate and has a gas barrier property. Can be a good oxide thin film.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, the wire is preferably formed of a metal or carbon that does not volatilize substantially as a main component when the hot wire is used. Regardless of the composition of the wire, an oxide thin film obtained by pyrolyzing and oxidizing a non-pyrophoric raw material can be obtained.

  In the method for manufacturing a plastic container coated with an oxide thin film according to the present invention, the wire is formed of a metal, a conductive metal compound, or carbon as a main component, and carbon, silicon, or metal when the hot wire is used. It is preferable that the element is volatilized and the carbon, silicon, or metal element is incorporated into the oxide thin film and becomes an additive component. By using a component derived from a non-pyrophoric raw material as a main component and a component derived from a wire as an additive component, the types of functional thin films that can be formed can be easily diversified.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, a mode in which the additive component functions as a color center can be selected. This is because the oxide thin film can be colored.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, the metal element functioning as the color center is cobalt, manganese, copper, iron, chromium, antimony, cadmium, sulfur, selenium, gold, nickel, Examples include uranium, vanadium, silver, molybdenum, tin, tungsten, bismuth or erbium.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, a mode in which the additive component functions as a crosslinking material in the oxide thin film can be selected. This is because the physicochemical stability of the oxide thin film can be improved or the refractive index can be adjusted.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, the case where the additive component that functions as the cross-linking material is sodium, potassium, lithium, lead, carbon, or titanium is included.

  In the method for manufacturing a plastic container coated with an oxide thin film according to the present invention, a volatile substance is applied or supported on the surface of the wire, and the volatile substance is volatilized when the hot wire is formed. The mode which is taken into the thin film and becomes an additive component can be selected. This is because it is possible to form an oxide thin film in which a component derived from a non-pyrophoric raw material is a main component and a component derived from a volatile substance supported on a wire is an additional component.

  In the method of manufacturing a plastic container coated with an oxide thin film according to the present invention, the wire is a metal containing at least one of carbon, silicon, and metal that volatilizes when the hot wire is used, or a conductive metal. A vapor formed of a compound or carbon as a main component and containing at least one component of carbon, silicon or metal volatilized from the hot wire is a non-spontaneous silicified organic compound or non-spontaneous ignition In addition to the non-pyrophoric raw material such as a functional aluminum-containing organic compound, it is possible to select an embodiment that becomes a non-pyrophoric raw material and that the vapor is oxidized to constitute one of the main components of the oxide thin film. This is because an oxide thin film in which a component derived from a non-pyrophoric material is a main component and a component derived from a wire is also a main component can be formed.

  In the method of manufacturing a plastic container coated with an oxide thin film according to the present invention, the wire is a metal containing at least one of carbon, silicon, and metal that volatilizes when the hot wire is used, or a conductive metal. The oxide thin film is formed of a compound or carbon as a main component, and the non-pyrophoric raw material is a vapor containing at least one component of carbon, silicon or metal volatilized from the hot wire, Can select an embodiment in which the vapor is an oxidized oxide thin film. This is because an oxide thin film whose main component is a wire-derived component can be formed. If it is the steam derived from a wire, safety | security will be improved further and a raw material introduction means will become simple. Moreover, the composition of the thin film can be easily controlled by adjusting the composition of the wire.

In the method for producing a plastic container coated with the oxide thin film to which the wire component is added according to the present invention, the vapor is a simple metal or a metal having a saturated vapor pressure of 10 ⁻⁴ Pa or more at 2000 ° C. or less. Vapor of a compound containing A sufficient film formation rate, for example, a film formation rate of 2.5 nm / second or more can be obtained.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, the vapor contains molybdenum, copper, aluminum, palladium, tungsten, silver, silicon, carbon, sodium, potassium, lithium, lead, titanium, or these. The oxide thin film is preferably a compound, and an oxide of molybdenum, copper, aluminum, palladium, tungsten, silver or silicon is the main component. Oxide thin films with different colors depending on the metal species are obtained. In addition to the main component vapor (molybdenum, copper, aluminum, palladium, tungsten, silver or silicon-containing vapor), these additional vapors (sodium, potassium, lithium, carbon, lead or titanium) (Steam containing) may be added.

  In the method for manufacturing a plastic container coated with an oxide thin film according to the present invention, a volatile substance is applied or supported on the surface of the wire, and the volatile substance is volatilized when the hot wire is formed. Incorporated into a thin film to become an additive component, or when a volatile substance is applied or supported on the surface of the wire to form the hot wire, the volatile substance evaporates, and the volatile substance becomes the wire. The aspect which becomes the main component of the oxide thin film as the non-pyrophoric raw material together with the vapor volatilized from can be selected. This is because an oxide thin film in which a component derived from a wire is a main component and a component derived from a volatile substance carried on the wire is an additive component can be formed. Moreover, it is because the component derived from a wire becomes a main component and the oxide thin film which becomes a main component also from the component derived from the volatile substance carry | supported by the wire can be formed into a film.

  In the method of manufacturing a plastic container coated with an oxide thin film according to the present invention, the non-pyrophoric raw material is a volatile substance applied or supported on the surface of the wire, and the volatilization occurs when the hot wire is used. A mode in which the active substance is volatilized and becomes the main component of the oxide thin film can be selected. This is because an oxide thin film whose main component is a component derived from a volatile substance can be formed. If derived from a volatile substance, the safety is high and the raw material introduction means is simplified.

  In the method for producing a plastic container coated with an oxide thin film according to the present invention, the volatile substance is preferably molybdenum, copper, aluminum, palladium, tungsten, silver, silicon, or a compound containing these. Oxide thin films with different colors depending on the metal species are obtained.

  According to the present invention, in a method for producing a gas barrier thin film-coated plastic container, a non-pyrophoric raw material and ozone are used in a container having a three-dimensional shape made of plastic at room temperature, and a thin film having a gas barrier property at a safe and high speed. Can be formed at a low temperature. This manufacturing method is an inexpensive manufacturing method that can be operated with a manufacturing apparatus that does not require expensive equipment.

  Embodiments of the present invention will be described with reference to the accompanying drawings. The embodiment described below is an example of the configuration of the present invention, and the present invention is not limited to the following embodiment. First, before explaining the method for manufacturing a plastic container coated with an oxide thin film according to this embodiment, a film forming apparatus to be used will be described with reference to FIGS. In addition, the same code | symbol was attached | subjected to the common site | part and components.

(First form: film formation on the inner surface of the container)
First, a film forming apparatus according to a first embodiment capable of forming an oxide thin film on the inner surface of a container will be described. 2A and 2B are schematic views showing the film forming apparatus according to the first embodiment, where FIG. 2A is a wire having a linear shape, FIG. 2B is a wire having a coil spring shape, and FIG. 2C is a zigzag wire. In the case of shape. 2B and 2C are partial enlarged views of the source gas supply pipe 23. FIG. Note that “FIG. 2” will be described as “FIG. 2A” unless otherwise specified. The film forming apparatus 100 shown in FIG. 2 is disposed in a vacuum chamber 6 that accommodates a plastic container 11, an exhaust pump (not shown) that evacuates the vacuum chamber 6, and a plastic container 11 that can be inserted and removed. A raw material gas supply pipe 23 made of an insulating and heat-resistant material for supplying a raw material gas (non-pyrophoric raw material) and ozone gas to the inside of the plastic container 11; a wire 18 supported by the raw material gas supply pipe 23; And a heater power source 20 that energizes the wire 18 to generate heat.

  In the vacuum chamber, a space for accommodating the plastic container 11 is formed, and this space becomes a reaction chamber 12 for forming a thin film. The vacuum chamber 6 includes a lower chamber 13 and an upper chamber 15 that is detachably attached to the upper portion of the lower chamber 13 and seals the inside of the lower chamber 13 with an O-ring 14. The upper chamber 15 has an upper and lower drive mechanism (not shown) and moves up and down as the plastic container 11 is carried in and out. The internal space of the lower chamber 13 is formed to be slightly larger than the outer shape of the plastic container 11 accommodated therein. The plastic container 11 is a beverage bottle, but may be a container used for other purposes.

  The inside of the vacuum chamber 6, particularly the inside of the lower chamber 13, has an inner surface 28 that is a black inner wall or an inner surface that has a surface roughness (Rmax) 0 in order to prevent reflection of light emitted as the wire 18 generates heat. It is preferable to have unevenness of 5 μm or more. The surface roughness (Rmax) is measured using, for example, a surface roughness measuring device (DEKTAX 3 manufactured by ULVAC TECHNO CORPORATION). In order to make the inner surface 28 a black inner wall, there are a plating process such as black nickel plating and black chrome plating, a chemical film treatment such as radiant and black dyeing, or a method of coloring by applying a black paint. Furthermore, it is preferable to provide a cooling means 29 such as a cooling pipe through which cooling water is flowed inside (not shown) or outside (FIG. 2) the vacuum chamber 6 to prevent the temperature of the lower chamber 13 from rising. The reason why the lower chamber 13 of the vacuum chamber 6 is particularly targeted is that when the wire 18 is inserted into the plastic container 11, the vacuum chamber 6 is in a state of being accommodated in the inner space of the lower chamber 13. By preventing the reflection of light and cooling the vacuum chamber 6, the temperature rise of the plastic container 11 and the accompanying thermal deformation can be suppressed. Furthermore, when a chamber 30 made of a transparent material through which the radiated light generated from the energized wire 18 can pass, for example, a glass chamber, is disposed inside the lower chamber 13, the temperature of the glass chamber in contact with the plastic container 11 is unlikely to rise. Therefore, the thermal influence on the plastic container 11 can be further reduced.

  The source gas supply pipe 23 is supported so as to hang downward at the center of the inner ceiling surface of the upper chamber 15. The non-pyrophoric raw material and ozone gas flow into the raw material gas supply pipe 23 through the flow rate adjusters 24a to 24b and the valves 25a to 25c. The source gas supply pipe 23 preferably has a cooling pipe and is integrally formed. As a structure of such a source gas supply pipe 23, for example, there is a double pipe structure. In the source gas supply pipe 23, the inner pipe line of the double pipe is a source gas channel 17, one end of which is connected to the gas supply port 16 provided in the upper chamber 15, and the other end is a gas blowout. It is a hole 17x. As a result, the raw material gas and the ozone gas are blown out from the gas blowing hole 17 x at the tip of the raw material gas flow path 17 connected to the gas supply port 16. On the other hand, the outer pipe line of the double pipe is a cooling water flow path 27 for cooling the source gas supply pipe 23, and plays a role as a cooling pipe. When the wire 18 is energized and generates heat to form a hot wire, the temperature of the source gas channel 17 rises. In order to prevent this, the cooling water circulates in the cooling water passage 27. That is, at one end of the cooling water flow path 27, cooling water is supplied from a cooling water supply means (not shown) connected to the upper chamber 15, and at the same time, the cooled cooling water is returned to the cooling water supply means. On the other hand, the other end of the cooling water passage 27 is sealed in the vicinity of the gas blowing hole 17x, and here, the cooling water is folded back. The entire raw material gas supply pipe 23 is cooled by the cooling water passage 27. By cooling, the thermal influence on the plastic container 11 can be reduced. Therefore, the material of the source gas supply pipe 23 is preferably an insulator and has a high thermal conductivity. For example, a ceramic tube formed of a material mainly containing aluminum nitride, silicon carbide, silicon nitride, or aluminum oxide, or a surface made of a material mainly containing aluminum nitride, silicon carbide, silicon nitride, or aluminum oxide Is preferably a coated metal tube. The wire can be energized stably, has durability, and can efficiently exhaust heat generated by the wire by heat conduction.

  The source gas supply pipe 23 may be configured as follows as another form (not shown). That is, the source gas supply pipe is a double pipe, the outer pipe is used as a source gas flow path, and a hole, preferably a plurality of holes, is formed in the side wall of the outer pipe. On the other hand, the inner pipe of the double pipe of the source gas supply pipe is formed by a dense pipe, and the cooling water flows as a cooling water flow path. The wire is routed along the side wall of the source gas supply pipe, but the part of the wire along the side wall is in contact with the source gas and ozone through the hole provided in the side wall of the outer pipe, and the pyrolyzed raw material is efficiently used. Can be oxidized well.

  If the gas blowing hole 17 x is too far from the bottom of the plastic container 11, it is difficult to form a thin film inside the plastic container 11. In the present embodiment, the length of the source gas supply pipe 23 is preferably formed such that the distance L1 from the gas blowing hole 17x to the bottom of the plastic container 11 is 5 to 50 mm. More preferably, the thickness is 15 to 30 mm. The uniformity of the film thickness is improved. By setting the distance to 5 to 50 mm, a uniform thin film can be formed on the inner surface of the plastic container 11. If the distance is larger than 50 mm, it is difficult to form a thin film on the bottom of the plastic container 11, and if the distance is smaller than 5 mm, it is difficult to blow out the source gas, or the inside of the plastic container 11 is near the gas blowing hole 17 x. Film formation tends to be excessive.

  The wire 18 is heated by energization to form a hot wire, thereby thermally decomposing the non-pyrophoric raw material and ozone gas. Oxidation of the non-pyrophoric raw material is promoted by the pyrolyzed ozone, and an oxide thin film is formed on the inner surface of the plastic container 11. In this embodiment, the wire 18 is preferably made of a metal, particularly an oxidation-resistant metal. For example, an Ir wire, a Re wire, a nichrome wire, a Pt wire or an Au wire, an Ir-based alloy wire, or a Re-based alloy. Line, Pt baseline or Au baseline. The wire 18 may be an object mainly composed of carbon, for example, carbon fiber. Since it has conductivity, it becomes possible to generate heat by energization. The wire 18 is not only a hot wire for heating means, but may also be a thermal catalyst by a catalytic chemical vapor deposition method. However, tungsten wires that are normally used as thermal catalyst bodies for catalytic chemical vapor deposition are deteriorated when oxidized, and should be avoided in an atmosphere containing ozone gas. The wire 18 is formed in a wiring shape, and one end of the wire 18 is connected to a connection portion 26 a that is provided below the fixed portion in the upper chamber 15 of the source gas supply pipe 23 and serves as a connection portion between the wiring 19 and the wire 18. The And it is supported with the insulating ceramic member 35 provided in the gas blowing hole 17x which is a front-end | tip part. Further, it is folded back and the other end of the wire 18 is connected to the connecting portion 26b. Thus, since the wire 18 is supported along the side surface of the source gas supply pipe 23, the wire 18 is disposed so as to be positioned substantially on the main axis of the internal space of the lower chamber 13. FIG. 2A shows the case where the wire 18 is arranged along the periphery of the source gas supply pipe 23 so as to be parallel to the axis of the source gas supply pipe 23. However, the source 18 starts from the connection portion 26a. It may be wound around the side surface of the gas supply pipe 23 in a spiral manner and supported by the insulating ceramics 35 fixed in the vicinity of the gas blowing hole 17x, and then folded back toward the connecting portion 26b. Here, the wire 18 is fixed to the source gas supply pipe 23 by being hooked on the insulating ceramic 35. In FIG. 2A, the case where the wire 18 is disposed outside the gas blowing hole 17x in the vicinity of the gas blowing hole 17x of the source gas supply pipe 23 is shown. As a result, the non-pyrophoric raw material and ozone gas blown out from the gas blowing hole 17x are likely to come into contact with the wire 18, so that the non-pyrophoric raw material can be efficiently decomposed and oxidized. Here, it is preferable that the wire 18 be disposed slightly away from the side surface of the source gas supply pipe 23. This is to prevent a rapid temperature rise of the source gas supply pipe 23. Moreover, the opportunity of contact with the non-pyrophoric raw material and ozone gas blown out from the gas blowing hole 17x and the non-pyrophoric raw material and ozone gas in the reaction chamber 12 can be increased. The outer diameter of the source gas supply pipe 23 including the wire 18 needs to be smaller than the inner diameter of the mouth portion 21 of the plastic container. This is because the source gas supply pipe 23 including the wire 18 is inserted from the mouth portion 21 of the plastic container. Therefore, if the wire 18 is separated from the surface of the source gas supply pipe 23 more than necessary, it will be easy to contact when the source gas supply pipe 23 is inserted from the mouth portion 21 of the plastic container. The lateral width of the wire 18 is suitably 10 mm or more and (inner diameter of the mouth part -6) mm or less in consideration of positional deviation when inserted from the mouth part 21 of the plastic container. Here, the inner diameter of the mouth portion 21 is approximately 21.7 to 39.8 mm.

  It is preferable that the upper limit temperature when the wire 18 is heated is not more than the temperature at which the wire softens. The temperature to operate as a hot wire varies depending on the material of the wire, and if it is Ir, the temperature can be raised to the softening temperature, but it is preferably, for example, 300 to 1800 ° C, more preferably 800 to 1100 ° C. preferable. In addition, by supplying ozone gas together with the non-pyrophoric raw material, a reaction at a low temperature of 300 ° C. can be performed as described above even when the hot wire method is used instead of the catalytic chemical vapor deposition method. Generally, the film quality tends to be better when the wire and the substrate are heated to some extent. However, the plastic substrate cannot be subjected to much heat load so as not to be thermally deformed. In this respect, if it is 800 to 1100 ° C., a problem caused by a thermal load from the wire does not occur for several hundred seconds or more for a container made of a general plastic material in the beverage / food field including PET resin, This is a preferable setting.

  Moreover, in order to increase the contact opportunity with a non-pyrophoric raw material and ozone gas, it is preferable that the wire 18 has the part which processed the wire into the coiled spring shape as shown in FIG.2 (b). The coil spring shape includes not only a cylindrical shape but also a conical shape, a barrel shape, or a hook shape, and further includes an unequal pitch shape in which the pitch between these windings is changed. Moreover, you may have the part which processed the wire into the zigzag line shape as shown in FIG.2 (c). Or you may have the part which processed the wire into the wavy line shape (not shown). In any of these forms, it is preferable that the wire 18 is disposed along the blowing direction of the non-pyrophoric raw material and ozone gas. This increases the chance that the non-pyrophoric raw material and the ozone gas 33 come into contact with the wire 18.

  About the fixing method of the source gas supply pipe | tube 23 of the wire 18, you may make it as follows as another form not shown. That is, the raw material gas supply pipe is a double pipe, and the outer pipe is formed of a porous pipe having a porosity of 10 to 40% using a raw material gas flow path. A wire may be directly wound around the porous outer tube. The stability of fixing the wire is improved, and the non-pyrophoric raw material and ozone gas are released from the side wall of the outer tube together with the gas blowing holes, so that the contact efficiency with the wire is improved. In this case, the inner pipe of the double pipe of the source gas supply pipe is formed by a dense pipe, and the cooling water flows as a cooling water flow path.

  FIG. 3 shows another form of the positional relationship between the wire 18 and the source gas supply pipe 23. In FIG. 3, the wire 18 is disposed in the source gas supply pipe 23. The wires 18 are arranged in two rows along the blowing direction of the non-pyrophoric raw material and the ozone gas 33. This increases the chance that the non-pyrophoric raw material and the ozone gas 33 come into contact with the wire 18. In addition, since the wire 18 is disposed inside the source gas supply pipe, the distance between the wire and the surface of the plastic container can be increased, so that occurrence of thermal deformation of the plastic container can be suppressed. As shown in FIG. 3, the wires 18 a and 18 b are preferably arranged such that the wire portions face in different directions. In FIG. 3, the wires are in a vertical and horizontal alternating relationship. In addition, although the shape of the cross section of the pipe | tube of the source gas supply pipe | tube 23 is a square in FIG. 3, circular, an ellipse, or a rectangle may be sufficient. Further, if the tube diameter is inserted from the mouth of the plastic container in order to form a film on the inner surface of the plastic container, it is necessary to make it smaller than the diameter of the mouth. On the other hand, when forming a film on the outer surface of the plastic container, it is preferable to increase the gas flow rate by increasing the tube diameter.

  A heater power source 20 is connected to the wire 18 via connection portions 26 a and 26 b and a wiring 19. By causing electricity to flow through the wire 18 by the heater power source 20, the wire 18 generates heat.

  Moreover, since the draw ratio at the time of shaping | molding of the plastic container 11 is small from the opening part 21 of a plastic container to the shoulder of a container, if the wire 18 which heats to high temperature is arrange | positioned nearby, it will be easy to raise | generate a deformation | transformation by heat. According to the experiment, the shoulder portion of the plastic container 11 is thermally deformed unless the positions of the connection portions 26a and 26b, which are the connection portions of the wiring 19 and the wire 18, are separated from the lower end of the mouth portion 21 of the plastic container by 5 mm or more. When it was raised and separated beyond 50 mm, it was difficult to form a thin film on the shoulder portion of the plastic container 11. Therefore, the wire 18 is preferably arranged so that the upper end thereof is located 5 to 50 mm below the lower end of the mouth portion 21 of the plastic container. That is, it is preferable that the distance L2 between the connecting portions 26a and 26b and the lower end of the mouth portion 21 is 5 to 50 mm. Thermal deformation of the shoulder portion of the container can be suppressed.

  An exhaust pipe 22 communicates with the internal space of the upper chamber 15 via a vacuum valve 8 so that air in the reaction chamber 12 inside the vacuum chamber 6 is exhausted by an exhaust pump (not shown). .

(Second form: film formation on the outer surface of the container)
Next, a film forming apparatus according to a second embodiment capable of forming a gas barrier thin film on the outer surface of the container will be described. FIGS. 4A and 4B are schematic views showing an embodiment of a film forming apparatus according to the second embodiment. FIG. 4A shows a case where the wire is linear, and FIG. 4B shows a case where the wire has a coil spring shape. However, FIG.4 (b) is the schematic of a wire. Note that “FIG. 4” will be described as “FIG. 4A” unless otherwise specified. The film forming apparatus 200 shown in FIG. 4 includes a vacuum chamber 60 that houses the plastic container 11, an exhaust pump (not shown) that evacuates the vacuum chamber 60, a wire 18 that is disposed around the plastic container 11, A raw material gas pipe 31 that supplies a non-pyrophoric raw material and ozone gas to a space outside the plastic container 11 in the vacuum chamber 60, and a heater power source 20 that energizes the wire 18 to generate heat. In the film forming apparatus 200, the mouth portion of the plastic container 11 is fixed by the bottle rotating mechanism 32, and the plastic container 11 is disposed so that the bottom does not contact inside the vacuum chamber 60.

  The vacuum chamber 60 has a space for accommodating the plastic container 11 therein, and this space serves as a reaction chamber 12 for forming a thin film. The vacuum chamber 60 includes a lower chamber 63 and an upper chamber 65 that is detachably attached to the upper portion of the lower chamber 63 and seals the inside of the lower chamber 63 with the O-ring 14. The upper chamber 65 has an upper and lower drive mechanism (not shown) and moves up and down as the plastic container 11 is carried in and out. The internal space of the lower chamber 63 is formed larger than the outer shape of the plastic container 11 so that the wire 18 can be disposed around the plastic container 11 accommodated therein.

  Here, the wire 18 is connected to a connection portion 79 a which is a connection portion between the wiring 19 and the wire 18 and one end thereof. In the film forming apparatus of FIG. 4, the wire 18 is linearly arranged from the inner side surface of the lower chamber 63 to the side surface facing the bottom surface, starting from the connection portion 79a, and then folded back from there. The other end is connected to the connecting portion 79b. In order to show the positional relationship between the wire 18 and the plastic container 11 at this time, a cross-sectional view taken along line A-A ′ is shown in FIG. 5. The wire 18 and the plastic container 11 are arranged at equal intervals on the left and right sides in the figure. The wire 18 is disposed so that the distance from the outer surface of the plastic container 11 is constant. The uniformity of the film thickness on the outer surface including the bottom of the container is improved. Further, two or more sets of wires 18 may be arranged. In this case, it is preferable that a plurality of wires 18 are arranged at rotationally symmetric positions with respect to the main axis of the plastic container. In order to show the positional relationship between the wire 18 and the plastic container 11 when two sets of the wires 18 are arranged, FIG. 6 shows a cross-sectional view along A-A ′. The wire 18 and the plastic container 11 are arranged at equal intervals on the top, bottom, left and right in the figure. In either case shown in FIG. 5 or FIG. 6, film formation can be improved by forming the plastic container 11 while rotating the plastic container 11 around the main axis by the bottle rotation mechanism 32. In particular, in the case of FIG. 5, since the wire 18 is one set, the effect of improving the uniformity of film formation is high. Although not shown, as another form of the arrangement of the wires 18, a spiral winding around the main axis of the plastic container 11 around the plastic container 11, or on a plurality of cross sections of the main axis of the plastic container 11 Then, there is a form in which each is wound in parallel and a plurality of ring-shaped wires are arranged in parallel. In any form, the uniformity of the film thickness can be improved. Of course, in this embodiment as well, the plastic container 11 may be formed by rotating the plastic container 11 around the main axis by the bottle rotation mechanism 32. Here, when arrange | positioning two or more sets of the wires 18, it is preferable to arrange | position 5 cm or more apart from each other. Without causing thermal damage to the plastic container, the oxidation of the non-pyrophoric raw material is promoted and the film thickness is easily obtained. The material of the wire 18 may be the same as that of the first embodiment.

  The wire 18 preferably has a portion obtained by processing a wire into a coil spring shape as shown in FIG. 4B in order to increase the chance of contact with the non-pyrophoric raw material and ozone gas. The coil spring shape includes not only a cylindrical shape but also a conical shape, a barrel shape, or a hook shape, and further includes an unequal pitch shape in which the pitch between these windings is changed. Moreover, you may have the part which processed the wire into the zigzag line shape (not shown). Or you may have the part which processed the wire into the wavy line shape (not shown). In any of these forms, it is preferable that the wire 18 is disposed along the blowing direction of the non-pyrophoric raw material and ozone gas. For example, a plurality of wires 18 are arranged, or the wires 18 have a vector component in the blowing direction of the non-pyrophoric raw material and ozone gas. This increases the opportunity for non-pyrophoric raw materials and ozone gas to come into contact with the wire.

  One end of the source gas pipe 31 is connected to a gas supply port 66 provided on the bottom surface of the lower chamber 63. A source gas supply pipe 73 is connected to the other end of the source gas pipe 31 and a branch in the middle thereof. In FIG. 4, a plurality of source gas supply pipes 73 are provided, each of which has a gas blowing hole 77x at the tip thereof. The non-pyrophoric raw material and the ozone gas 33 flow into the raw material gas supply pipe 73 through the raw material gas pipe 31, the gas supply port 66, the flow rate regulators 24a to 24b, and the valves 25a to 25c. Thereby, the non-pyrophoric raw material and the ozone gas 33 are blown out from the gas blowing holes 77x. The gas blowing holes 77x are all directed to the outer surface of the plastic container 11, and the non-pyrophoric raw material and ozone gas can be sprayed to any part of the outer surface. And the wire 18 is arrange | positioned at the exit side of the gas blowing hole 77x. Thereby, since many contacts with the wire 18, a non-pyrophoric raw material, and ozone gas arise, the oxidation of a non-pyrophoric raw material can be promoted.

  The source gas supply pipe 73 is a single metal pipe. As in the case of the first embodiment, a double pipe may be used for flowing cooling water. Moreover, it is good also as the metal pipe | tube with which the surface was coat | covered with the ceramic pipe | tube similar to the case of a 1st form, or ceramic materials.

  The length of the source gas supply pipe 73 is preferably formed such that the distance L3 from the gas blowing hole 77x to the outer surface of the plastic container 11 is 5 to 50 mm. A uniform thin film can be formed on the outer surface of the plastic container 11 at a distance of 5 to 50 mm. When the distance is larger than 50 mm, it is difficult to form a thin film on the outer surface of the plastic container 11, and when the distance is smaller than 5 mm, it is difficult to blow out the source gas.

  As another form of the positional relationship between the wire 18 and the source gas supply pipe 73, for example, a wire may be arranged in the source gas supply pipe as in the case of FIG. At this time, if the inner diameter of the source gas supply pipe is increased to, for example, 10 mm or more, the uniformity of the film distribution is improved. By bringing the non-pyrophoric raw material and ozone gas into contact with the wire in the pipe of the raw material gas supply pipe, the pyrolyzed non-pyrophoric raw material can be blown out from the raw material gas supply pipe. Since the wire is disposed inside the raw material gas supply pipe, the distance between the wire and the surface of the plastic container can be increased, so that occurrence of thermal deformation of the plastic container can be suppressed.

  In order to prevent thermal deformation of the plastic container 11, it is preferable to provide a cooling means 29 such as a cooling pipe through which cooling water flows inside or outside the vacuum chamber 60 to prevent the temperature of the lower chamber 63 from rising.

  A heater power source 20 is connected to the wire 18 via connection portions 79 a and 79 b and a wiring 19. By causing electricity to flow through the wire 18 by the heater power source 20, the wire 18 generates heat. Also in this form, it is preferable that the operating temperature of the wire 18 shall be 300-1800 degreeC, and it is more preferable that it is 800-1100 degreeC.

  An exhaust pipe 22 communicates with the internal space of the upper chamber 65 via a vacuum valve 8 so that air in the reaction chamber 12 inside the vacuum chamber 60 is exhausted by an exhaust pump (not shown). . Although not shown, in both the first and second embodiments, the ozone gas is silently discharged from, for example, an oxygen gas from an oxygen cylinder using a commercially available relatively inexpensive ozone generator. You may obtain and supply from the gas cylinder (Iwatani Corp. make) which contains ozone gas stably.

  In any of the film forming apparatuses of the first and second embodiments, the wire 18 becomes a hot wire only by passing an electric current, and can oxidize a non-pyrophoric raw material thermally decomposed by ozone. An oxide thin film can be formed on a large number of plastic containers at a time. FIG. 7 is a conceptual diagram of a film forming apparatus for simultaneously forming an oxide thin film on the inner surfaces of a plurality of plastic containers. In FIG. 7, a large number of plastic containers 11 are positioned and arranged in one lower chamber 13, and wires 18 and source gas supply pipes 23 similar to those in FIG. 2 are inserted into the respective mouths of the plastic containers 11 to form oxides. A thin film is formed. FIG. 8 is a conceptual diagram of a film forming apparatus for simultaneously forming a gas barrier thin film on the outer surfaces of a plurality of plastic containers 11. In FIG. 8, a large number of plastic containers 11 are positioned and arranged in one lower chamber 63, and the wires 18 are arranged so as to surround each plastic container 11, and the non-pyrophoric raw material is supplied from the raw material gas supply pipe 73. Then, ozone gas is brought into contact with the wire 18 and then sprayed onto the plastic container 11. Here, the mouth is fixed to the bottle rotation mechanism 32, and a thin film is formed on the outer surface of the plastic container 11 while rotating. Furthermore, FIG. 9 is a conceptual diagram of a film forming apparatus for forming a gas barrier thin film simultaneously on the outer surfaces of a plurality of plastic containers in-line. In FIG. 9, the plastic container is moved by the conveyor in the order of the bottle alignment chamber 40, the exhaust chamber 41, the thin film formation chamber 42, the atmospheric leak chamber 43 and the take-out chamber 44 in the vacuum chamber. The outside of the vacuum chamber is under atmospheric pressure, but the thin film forming chamber 42 is kept at a constant pressure reduced by a differential pressure mechanism. The exhaust chamber 41 and the atmospheric leak chamber 43 are included in the differential pressure mechanism. In the thin film forming chamber 42, wires 18 are arranged along the side walls of the chamber. The plastic container approaches a desired distance, for example, 5 to 50 mm, between the wire 18 and the surface of the plastic container when passing through the conveyance path in the vacuum chamber. In the thin film forming chamber 42, the source gas is blown out toward the wire 18 to fill the chamber with the non-pyrophoric raw material and ozone, and film formation is performed when the plastic container 11 passes through the thin film forming chamber 42. In any of the film forming apparatuses of the first and second embodiments, the same vacuum chamber can be used even if the shape of the container is different, a high frequency power source is unnecessary, and a plurality of containers are formed in one vacuum chamber. It can be formed into a film. Thereby, the apparatus becomes cheaper than a film forming apparatus using a high frequency power source.

  In both the first and second film forming apparatuses, the non-pyrophoric raw material and the ozone gas 33 become hot air, so that the plastic container 11 is easily deformed by heat. Therefore, it is preferable to provide a container cooling means. 10A and 10B are conceptual diagrams for explaining the container cooling means. FIG. 10A shows a case where a film is formed on the inner surface of the plastic container, and FIG. 10B shows a case where a film is formed on the outer surface of the plastic container. As shown in FIG. 10A, the non-pyrophoric raw material that is hot air and the ozone gas 33 are sprayed on the inside of the plastic container 11, and the film forming apparatus of the first form is cooled on the outer surface of the plastic container 11. It is preferable to have a container cooling means 51 to which the liquid or gas 50 is applied. The container cooling means 51 is a water tank when the plastic container 11 is immersed in a liquid such as water, and is a shower when the liquid such as water is showered on the plastic container 11. Further, when a gas such as cooling nitrogen gas or cooling carbon dioxide gas is blown into the plastic container 11, it is a blower. The cooling nitrogen gas can be easily obtained by using liquid nitrogen and the cooling carbon dioxide gas by using dry ice. As shown in FIG. 10B, the non-pyrophoric raw material that becomes hot air and the ozone gas 33 are sprayed toward the outer surface of the plastic container 11. It is preferable to have a container cooling means 51 for applying the cooled liquid or gas 50. The container cooling means 51 is a liquid filling device when filling the plastic container 11 with a liquid such as water, and a blower when blowing a gas such as cooling nitrogen gas or cooling carbon dioxide gas onto the inner surface of the plastic container 11. It is.

  FIG. 11 shows another embodiment of the thin film forming chamber 42 of FIG. On the side wall of the thin film deposition chamber 42, the source gas supply pipes 23 and the container cooling means 51 are alternately arranged along the moving direction of the plastic container 11. The plastic container 11 is moved by a conveyor (conveyance path, not shown) and is rotated. Here, the source gas supply pipe 23 uses the type shown in FIG. The container cooling means 51 uses a type in which cooled nitrogen gas is blown. When the plastic container 11 is moved while being rotated by the conveyor, the raw material gas activated by the wire is blown from the raw material gas supply pipe 23, and then the cooled nitrogen gas is blown by the container cooling means 51. These are performed alternately. At this time, thin film formation proceeds.

  Next, the manufacturing method of the plastic container which coat | covered the oxide thin film which concerns on this embodiment is demonstrated. If the film forming apparatus 100 of FIG. 2 is used, it is possible to coat the oxide thin film on the inner surface of the plastic container. On the other hand, if the film forming apparatus 200 of FIG. It is possible to coat the surface. Since these two film forming methods have common processes, unless otherwise specified, a film forming method for coating an oxide thin film on the inner surface of a plastic container using the film forming apparatus 100 of FIG. 2 as a representative example. Will be explained. Note that an oxide thin film may be formed on both the inner surface and the outer surface of the plastic container using the film formation apparatus 100 and the film formation apparatus 200.

  The manufacturing method of the plastic container coated with the oxide thin film according to the present embodiment includes a step of setting the inside of the vacuum chamber 6 containing the plastic container 11 to a predetermined pressure equal to or lower than the atmospheric pressure (hereinafter referred to as a decompression step), and a vacuum chamber. 6, a process of energizing the wire 18 arranged inside 6 to generate heat to a predetermined temperature or more to form a hot wire (hereinafter referred to as a hot wire process), and a silicon or metal element supplied into the vacuum chamber 6 A process of heating the non-pyrophoric raw material containing ozone as a constituent element and the ozone gas 33 with the hot wire 18 and then contacting the inner surface of the plastic container 11 to form an oxide thin film derived from the non-pyrophoric raw material ( Hereinafter referred to as a film forming step).

(Attaching the container to the deposition system)
First, a vent (not shown) is opened to open the vacuum chamber 6 to the atmosphere. In the reaction chamber 12, the plastic container 11 is inserted and accommodated from the upper opening of the lower chamber 13 with the upper chamber 15 removed. Thereafter, the positioned upper chamber 15 is lowered, and the source gas supply pipe 23 attached to the upper chamber 15 and the wire 18 fixed thereto are inserted into the plastic container 11 from the mouth portion 21 of the plastic container. Then, the upper chamber 15 is brought into contact with the lower chamber 13 via the O-ring 14, whereby the reaction chamber 12 is made a sealed space. At this time, the distance between the inner wall surface of the lower chamber 13 and the outer wall surface of the plastic container 11 is kept substantially uniform, and the distance between the inner wall surface of the plastic container 11 and the wire 18 is also kept substantially uniform. I'm leaning.

  The container according to the present invention 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. Examples of the filling material in the plastic container according to the present invention include beer, sparkling liquor, carbonated drink, fruit juice drink, and soft drink. Moreover, either a returnable container or a one-way container may be used.

  Resin used when molding the plastic container 11 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 It can be exemplified fat. Among these, PET is particularly preferable.

(Decompression step)
Next, after closing the vent (not shown), the exhaust pump (not shown) is operated and the vacuum valve 8 is opened, whereby the air in the reaction chamber 12 is exhausted. At this time, not only the internal space of the plastic container 11 but also the space between the outer wall surface of the plastic container 11 and the inner wall surface of the lower chamber 13 is evacuated and evacuated. That is, the entire reaction chamber 12 is exhausted. The pressure in the reaction chamber 12 is reduced until it reaches a required pressure, for example, 1 to 100 Pa, preferably 10 to 100 Pa. This requires an exhaust time at a pressure of less than 1 Pa, and the film formation rate may decrease, resulting in an increase in film formation cost. If a pressure higher than 100 Pa is sufficient, the pyrolyzed / oxidized non-pyrophoric raw material may be particleized in the gas phase.

(Hot wire process)
Next, the wire 18 is energized to generate heat above a predetermined temperature to form a hot wire. The predetermined temperature is, for example, 300 to 1800 ° C. although it depends on the type of non-pyrophoric raw material. It is more preferable that it is 800-1100 degreeC. Moreover, the hot wire 18 is arrange | positioned so that the distance with the inner surface of the plastic container 11 may be 5-50 mm.

(Film formation process)
Thereafter, a non-pyrophoric raw material is supplied at a predetermined flow rate by the gas flow rate adjuster 24a, and ozone gas is supplied at a predetermined flow rate by the gas flow rate adjuster 24b. The non-pyrophoric raw material and the ozone gas are blown out through the raw material gas supply pipe 23 toward the hot wire 18 that generates heat from the gas blowing hole 17x to 300 to 1800 ° C. in the plastic container 11 that has been decompressed to a predetermined pressure. The The non-pyrophoric raw material and ozone gas heated by the hot wire are immediately brought into contact with the inner surface of the plastic container 11. From the initial stage of film formation, ozone is decomposed by the hot wire 18 into radical oxygen, and the pyrolyzed non-pyrophoric raw material is oxidized. Then, an oxide thin film derived from a non-pyrophoric raw material is formed on the inner surface of the plastic container 11.

In the present invention, the non-pyrophoric raw material is a raw material that does not ignite spontaneously, does not cause a violent reaction in the air, and generates an oxide when oxidized as described above. The non-pyrophoric raw material may be solid, liquid, or gas. As long as it is a raw material containing silicon as a constituent element, a non-pyrophoric silicified organic compound is preferable. On the other hand, examples of pyrophoric materials include silane-based materials such as monosilane, disilane, and trisilane. An SiO _x thin film can be formed as an oxide thin film by using a silicified organic compound such as trimethylsilane as a non-pyrophoric raw material and thermally decomposing with a hot wire 18.

  As the non-pyrophoric silicified organic compound, for example, trimethylsilane, hexamethyldisiloxane, phenylsilane, or hexamethylsilazane is preferable. Also, dimethoxy (methyl) silane, ethoxydimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, tetramethoxysilane, tetramethylsilane, dimethoxymethylsilane, ethoxyquintrimethylsilane, diethoxymethylsilane, ethoxydimethylvinylsilane, allyltrimethylsilane , Diethoxydimethylsilane, tolylethylsilane, hexamethyldisilane, diethoxymethylvinylsilane, triethoxymethylsilane, triethoxyvinylsilane, bis (trimethylsilyl) acetylene, tetraethoxysilane, trimethoxyphenylsilane, γ-glycidoxypropyl ( Dimethoxy) methylsilane, γ-glycidoxypropyl (trimethoxy) methylsilane, γ-methacryloxypropyl (dimethoxy) methyl Lan, γ-methacryloxypropyl (trimethoxy) silane, dihydroxydiphenylsilane, diphenylsilane, triethoxyphenylsilane, tetraisopropoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, tetra-n-butoxysilane, tetraphenoxysilane or poly (Methylhydrogensiloxane) may also be used.

Non-pyrophoric raw materials include, in addition to the aforementioned non-pyrophoric silicified organic compounds, raw materials containing metal elements as constituent elements, for example, non-pyrophoric metal element-containing organics such as organometallic compounds and metal alkoxides. It may be a compound. If the metal element is aluminum, for example, it is preferably a non-pyrophoric aluminum-containing organic compound, more preferably an alkoxide-based raw material. For example, tritertiary butoxy aluminum (Al (t-OC ₄ H ₉ ) ₃ ), triethoxy aluminum (Al (OC ₂ H ₅ ) ₃ ), triisopropoxy aluminum (Al (i-OC ₃ H ₇ ) ₃ ), Trisecondary butoxy aluminum (Al (sec-OC ₄ H ₉ ) ₃ ), trisacetylacetonate aluminum (Al (C ₅ H ₇ O ₂ ) ₃ ) or trisdipivaloylmethanate aluminum (Al (C ₁₁ H ₁₉₎ O ₂ ) ₃ ). On the other hand, as a pyrophoric raw material, there is trimethylaluminum. For example, triisopropoxyaluminum is used as the non-pyrophoric raw material, and the AlO _x thin film can be formed as the oxide thin film by thermal decomposition with the hot wire 18.

In the present embodiment, the reason for supplying the non-pyrophoric raw material and ozone together is as follows. First of all, it is necessary to form a film in a plastic container having a three-dimensional shape, and since it is necessary to form a film at a low temperature as long as a plastic material is used, a highly efficient precipitation reaction can be performed in a three-dimensional shape even at a low temperature. Must be realized on the surface. Second, when an oxide thin film is formed by pyrolyzing and oxidizing a highly safe non-pyrophoric raw material, according to the study of the present inventors, the non-pyrophoric raw material and oxygen are combined together. No oxide was deposited even when supplied. Therefore, by supplying ozone with extremely strong oxidizing power together with the non-pyrophoric raw material, it is possible to thermally decompose and oxidize the non-pyrophoric raw material to efficiently generate an oxide thin film. It has been found that a film can be formed on a plastic container having a shape. It is considered that ozone decomposes as shown in chemical formula 1 when heated to ultraviolet rays or 200 ° C. or higher.
(Chemical Formula 1) O ₃ → O ₂ + O.
Therefore, when ozone is heated with the hot wire 18, it decomposes | disassembles according to Chemical formula 1, and radical oxygen exhibits strong oxidizing power. At the same time, since the non-pyrophoric raw material is heated by the hot wire 18, the non-pyrophoric raw material is thermally decomposed by the heat of the wire or decomposed by the catalytic action of the wire and oxidized by radical oxygen. As a result, an oxide thin film derived from a non-pyrophoric raw material is generated. Here, the hot wire 18 has at least two functions of (1) converting ozone into radical oxygen according to chemical formula 1, and (2) heating and pyrolyzing non-pyrophoric raw materials or decomposing by catalytic action. . The hot wire 18 is not necessarily required to have a catalytic action in the catalytic chemical vapor deposition method, and the hot wire 18 only needs to be able to heat the non-pyrophoric raw material and ozone simultaneously. Of course, the form which uses the hot wire 18 which has a catalytic action and promotes thermal decomposition of a non-pyrophoric raw material by the catalytic action is not excluded from the present invention.

  As described above, ozone is supplied by a commercially available ozonizer or ozone cylinder.

  A diluent gas may be mixed with the non-pyrophoric raw material and ozone. As the dilution gas, for example, an inert gas such as argon or helium or a gas inert to a chemical reaction during film formation is used. It can be used for adjusting the concentration of a non-pyrophoric raw material and adjusting the pressure in a vacuum chamber.

  The supply amount of the ozone gas is preferably an amount such that carbon remaining in the oxide thin film is substantially zero, for example, a flow rate 5 to 20 times that of the non-pyrophoric substance. If the supply amount of ozone gas is small, carbon remains in the oxide thin film. If the supply amount is sufficient or more, carbon does not remain in the oxide thin film. When the carbon remaining in the oxide thin film is substantially zero, the gas barrier property is the best.

  Here, the supply amount of ozone gas is first set to an amount in which carbon remains in the oxide thin film at the start of film formation of the oxide thin film (for example, 0.5-2. (The flow rate is 0 times) and then the supply amount is increased so that the carbon remaining in the oxide thin film becomes substantially zero (for example, the flow rate is 5 to 20 times that of non-pyrophoric substances). ) At this time, the oxide thin film has a distribution in which the carbon content decreases toward the surface along the thickness direction, and becomes a gradient composition thin film. The oxide thin film has good adhesion to the substrate when carbon remains in the oxide thin film, while the gas barrier property is best when carbon remaining in the oxide thin film is substantially zero. Shows physical properties. For this reason, carbon is left in the oxide thin film on the surface of the substrate, and a gradient composition film is formed so that carbon does not remain on the surface of the oxide thin film. An oxide thin film with good properties can be obtained.

  In the present embodiment, it is preferable to irradiate the plastic container 11 with ultraviolet rays during film formation (ultraviolet irradiation means is not shown). The surface of the plastic container 11 can be sterilized. Moreover, the decomposition of ozone is promoted by the irradiation of ultraviolet rays to increase the oxidizing power, and as a result, the oxidation of the non-pyrophoric raw material can be promoted. At this time, the non-pyrophoric raw material and the ozone gas are heated by the hot wire, but the reaction can be efficiently advanced without hindering the irradiation of ultraviolet rays by the hot wire.

  When the wire 18 is a hot wire, the wire 18 is preferably formed mainly of a metal or carbon that does not substantially volatilize. Here, the metal is preferably an oxidation-resistant metal. For example, Ir, Re, Ni, Pt or Au. An oxide thin film derived from a non-pyrophoric raw material with few impurities can be formed.

On the other hand, the volatile component derived from the wire may be incorporated into the oxide thin film as an additive component, not as an impurity. In order to perform the manufacturing method of such a form, it carries out as follows. The wire 18 is formed of a metal, a conductive metal compound, or carbon as a main component, and volatilizes carbon, silicon, or a metal element when used as a hot wire, and the carbon, silicon, or metal element is converted into an oxide thin film. It may be taken in and become an additive component. This is an effective technique when an additive component is intentionally introduced into the oxide thin film. Specific examples of the metal are, for example, molybdenum, copper, aluminum, or palladium. When a hot wire is formed, these metal elements are volatilized and taken into the oxide thin film to become an additive component. Specific examples of the conductive metal compound include, for example, FeC or FeCrC. When the hot wire is formed, the carbon volatilizes and is taken into the oxide thin film and becomes an additive component. As a specific example of a form in which the wire 18 is formed of a metal as a main component and volatilizes silicon when it is used as a hot wire, Si is sputtered on the surface of a wire of a non-volatile metal such as Ir, Pt or NiCr. And there is a coated wire. When hot wire is used, silicon volatilizes and is taken into the oxide thin film to become an additive component. If the wire 18 is a wire containing carbon as a main component, for example, carbon fiber, the carbon volatilizes when it is used as a hot wire, and is taken into the oxide thin film and becomes an additive component. When carbon, silicon, or a metal element is incorporated as an additive component into the oxide thin film, the physical properties of the oxide thin film are improved. For example, when silicon is incorporated as an additive component into an oxide thin film, such as an AlO _x thin film, flexibility is improved while maintaining gas barrier properties. The volatilized metal element is preferably taken into an oxide thin film such as a SiO _x thin film or an AlO _x thin film to form a color center. The oxide thin film can be colored. Specific examples of metal elements that function as color centers include, for example, cobalt, manganese, copper, iron, chromium, antimony, cadmium, sulfur, selenium, gold, nickel, uranium, vanadium, silver, molybdenum, tin, tungsten, and bismuth. Or erbium.

In the present embodiment, it is preferable that the additive component functions as a cross-linking material in the oxide thin film. The physicochemical stability of the oxide thin film can be improved, or the refractive index can be adjusted. Specific examples of the additive component that functions as a cross-linking material include sodium, potassium, lithium, lead, carbon, and titanium. For example, if the oxide thin film is a SiO _x thin film, it can enter the network structure of SiO _x as a network decoration oxide or intermediate oxide by adding sodium, potassium or lithium, and physical chemistry such as thermal expansion coefficient and hardness Can be adjusted. Similarly, if lead is added, the refractive index can be increased. Similarly, when titanium is added, alkali resistance is improved. Similarly, if carbon is added, flexibility can be imparted.

As another mode of incorporating the oxide thin film as an additive component, for example, the following is performed. That is, a volatile substance is applied or supported on the surface of the wire 18 to volatilize the volatile substance when it is used as a hot wire, and is taken into the oxide thin film to be an additive component. It is possible to form an oxide thin film in which a component derived from a non-pyrophoric raw material is a main component and a component derived from a volatile substance supported on a wire is an additional component. Specific examples of the volatile substance are molybdenum, copper, aluminum, palladium, tungsten, silver, silicon, or a compound containing these. The oxide thin film can be colored. Further, by incorporating silicon as an additive component into the AlO _x thin film, flexibility is improved while maintaining gas barrier properties. In addition, in this form, there exists a form in which the component of the wire 18 does not volatilize, and a form in which it volatilizes. In the latter case, both volatile materials and volatiles from the wire are incorporated into the oxide thin film as additive components.

  Furthermore, in this embodiment, it is good also as a form which forms the oxide thin film into which the component derived from a non-pyrophoric raw material becomes a main component, and the component derived from a wire also becomes a main component. That is, in such a form, the wire 18 is formed mainly of a metal, a conductive metal compound, or carbon containing at least one of carbon, silicon, and metal that volatilizes when it is used as a hot wire. And vapor containing at least one component of carbon, silicon, or metal volatilized from the hot wire is a non-pyrophoric silicified organic compound or a non-pyrophoric aluminum-containing organic compound. There is a form that becomes a non-pyrophoric raw material together with the pyrophoric raw material, and the steam is oxidized to constitute one of the main components of the oxide thin film. Specific examples of the metal are, for example, molybdenum, copper, aluminum, or palladium. These metal elements volatilize when used as hot wires, and vapors containing these metal elements become non-pyrophoric raw materials that are oxidized and contain non-pyrophoric silicified organic compounds or non-pyrophoric aluminum Together with non-pyrophoric raw materials such as organic compounds, it becomes one of the main components of oxide thin films. As a specific example of a form in which the wire 18 is formed of a metal as a main component and volatilizes silicon when it is used as a hot wire, Si is sputtered on the surface of a wire of a non-volatile metal such as Ir, Pt or NiCr. And there is a coated wire. Silicon is volatilized when used as a hot wire, and this vapor becomes a non-pyrophoric raw material that is oxidized and non-pyrophoric, such as non-pyrophoric silicified organic compounds or non-pyrophoric aluminum-containing organic compounds Together with the raw material, it becomes one of the main components of the oxide thin film. The conductive metal compound is not used alone, but is used together with the two non-pyrophoric raw materials (a vapor containing a metal element and a vapor containing silicon). Specific examples of the conductive metal compound include, for example, FeC or FeCrC. When it is used as a hot wire, carbon is volatilized, oxidized, and taken into the oxide thin film as an additive component.

The method of supplying the non-pyrophoric raw material described above includes a form of supplying via the raw material gas supply pipe 23. Here, as the method of supplying the non-pyrophoric raw material, the raw material gas supply pipe 23 is used. Another embodiment 1 is described in which only ozone gas is allowed to flow through the source gas supply pipe 23 without being supplied via the source gas. In other words, the wire 18 is a wire formed of a metal, a conductive metal compound, or carbon containing at least one of carbon, silicon, or metal that volatilizes as a hot wire as a main component. Then, when it becomes a hot wire, the vapor | steam containing at least any 1 type of component of the carbon volatilized from the hot wire becomes a non-pyrophoric raw material. Specific examples of the metal are, for example, molybdenum, copper, aluminum, or palladium. When a hot wire is formed, these metal elements are volatilized, and a vapor containing these metal elements becomes a non-pyrophoric raw material, which is oxidized and becomes a main component of an oxide thin film of the metal element. As a specific example of a form in which the wire 18 is formed of a metal as a main component and volatilizes silicon when it is used as a hot wire, Si is sputtered on the surface of a wire of a non-volatile metal such as Ir, Pt or NiCr. And there is a coated wire. Silicon is volatilized when it is used as a hot wire, and this vapor becomes a non-pyrophoric raw material that is oxidized and becomes the main component of the SiO _x thin film. The conductive metal compound is not used alone, but is used together with the two non-pyrophoric raw materials (a vapor containing a metal element and a vapor containing silicon). Specific examples of the conductive metal compound include, for example, FeC or FeCrC. When it is used as a hot wire, carbon is volatilized, oxidized, and taken into the oxide thin film as an additive component. If it is the steam derived from a wire, safety | security will be improved further and a raw material introduction means will become simple. Moreover, the composition of the thin film can be easily controlled by adjusting the composition of the wire. Moreover, the raw material introduction means is simplified. The vapor derived from the wire is preferably a simple substance of a metal having a saturated vapor pressure of 10 ⁻⁴ Pa or more at a temperature of 2000 ° C. or less or a vapor of a compound containing the metal. A sufficient film formation rate, for example, a film formation rate of 2.5 nm / second or more can be obtained.

  As said vapor | steam, it is the vapor | steam (1) containing molybdenum, copper, aluminum, palladium, tungsten, silver, or silicon, for example. At this time, the oxide thin film becomes an oxide thin film of molybdenum, copper, aluminum, palladium, tungsten, silver, or silicon by the oxidizing action of ozone. Moreover, the vapor | steam (2) containing carbon, sodium, potassium, lithium, lead, or titanium may exist simultaneously with the said vapor | steam (1). The vapor (1) is oxidized to form an oxide thin film, and elements contained in the vapor (2) are taken into the oxide thin film as an additive component.

In another embodiment 1 in which only ozone gas is allowed to flow through the source gas supply pipe 23 without being supplied via the source gas supply pipe 23, a volatile substance is applied to or supported on the surface of the wire to form a volatile substance. May be volatilized and incorporated into the oxide thin film to serve as an additive component. An oxide thin film in which a component derived from a wire is a main component and a component derived from a volatile substance carried on the wire is an additive component can be formed. Alternatively, a volatile substance is applied or supported on the surface of the wire, and when the hot wire is formed, the volatile substance is volatilized. You may make it become a main component. An oxide thin film in which a component derived from a wire is a main component and a component derived from a volatile substance carried on the wire is also a main component can be formed. At this time, the oxide constituting the oxide thin film becomes a single-component oxide thin film such as a SiO _x thin film or an AlO _x thin film if the main component derived from the non-pyrophoric raw material and the main component derived from the wire are the same. If the main component derived from the non-pyrophoric raw material is different from the main component derived from the wire, a double oxide oxide thin film is obtained. An example of the double oxide is SiMo _x O _y . The volatile substance is a substance that becomes an oxide when oxidized, for example, molybdenum, copper, aluminum, palladium, silicon, or a compound containing these, and these are preferably powders.

  Furthermore, as a method for supplying the non-pyrophoric raw material, another embodiment 2 in which only ozone gas is allowed to flow through the raw material gas supply pipe 23 without being supplied through the raw material gas supply pipe 23 will be described. A volatile substance coated or supported on the surface of the wire 18 is used as a non-pyrophoric material. If it is this form, when the wire 18 is used as a hot wire, a volatile substance will volatilize. The volatile substance is a substance that becomes an oxide when oxidized in the same manner as described above, for example, molybdenum, copper, aluminum, palladium, silicon, or a compound containing these, and these are preferably powders. . An oxide thin film of these elements is obtained. And the oxide thin film originating in a volatile substance is safely obtained by the oxidation action of ozone. Moreover, the raw material introduction means is simplified. In addition to a colorless and transparent oxide thin film such as a silicon oxide film, an oxide thin film exhibiting color can be obtained.

  When sodium, potassium or lithium is volatilized as a volatile substance, it is unstable as a simple substance, so these salts such as carbonates and oxalates are supported on wires.

(Finish film formation)
When the thin film reaches a predetermined thickness, the supply of the non-pyrophoric raw material and the ozone gas 33 is stopped, the reaction chamber 12 is evacuated again, a leak gas (not shown) is introduced, and the reaction chamber 12 is brought to atmospheric pressure. To do. Thereafter, the upper chamber 15 is opened and the plastic container 11 is taken out. The thickness of the thin film depends on the type of the wire 18, the pressure in the plastic container 11, the supply gas flow rate, the time during which the non-pyrophoric raw material and the ozone gas 33 are sprayed on the wire 18, the type of the non-pyrophoric raw material, and the like. 5 to 100 nm is preferable. According to the said embodiment, the film-forming speed | rate is as high as 2.5-4.0 nm / second, for example. When the oxygen permeability of the plastic container coated with the oxide thin film was measured, it was reduced to one-half to one-fifth compared with an uncoated plastic container, and an improvement in barrier properties could be confirmed.

  When forming an oxide thin film on the outer surface of the plastic container 11, it is preferable to perform the film formation in a state where the plastic container 11 is rotated by the bottle rotation mechanism 32 in order to improve the uniformity of the film. .

  Next, an embodiment of mass production in the method for manufacturing a plastic container coated with an oxide thin film according to this embodiment will be described. In the method for manufacturing a plastic container coated with an oxide thin film according to the present embodiment, the plastic container 11 is housed in the vacuum chamber 6 that is set to a predetermined pressure (eg, 10 to 100 Pa) that is equal to or lower than the atmospheric pressure in the decompression step. In order to achieve this state, a process of adding the plastic container 11 into the vacuum chamber 6 via a differential pressure mechanism is added. Since the plastic containers 11 are continuously conveyed at predetermined intervals one after another in the conveyance path, it is preferable to use a type having a differential pressure mechanism shown in FIG. 9 for example as a vacuum chamber rather than a batch type. And in order to make the non-pyrophoric raw material heated with the hot wire and ozone contact the surface of the plastic container 11 efficiently, the plastic container 11 is attached to the wire 18 installed in the conveyance path in the vacuum chamber. A step of transporting on the transport path is added so that the surface of the plastic container 11 approaches a desired distance (for example, 5 to 50 mm). Further, a step of taking out the plastic container after film formation, that is, a step of transporting the plastic container 11 out of the vacuum chamber via a differential pressure mechanism is further added. By adding the above steps, it becomes possible to mass-produce plastic containers coated with an oxide thin film efficiently.

(Example 1)
Film formation was performed on the inner surface of a round 500 ml PET bottle as a plastic container 11 using the film formation apparatus 100 shown in FIG. The wall thickness of the container wall was about 0.3 mm. An iridium wire was used as the wire 18 and 1.5 sccm of trimethylsilane was supplied as a non-pyrophoric material. Ozone was diluted to 10% with oxygen to obtain a mixed gas, and this mixed gas was supplied at 100 sccm. The distance between the wire 18 and the bottom surface inside the bottle was 30 mm. The distance between the wire 18 and the inner side surface of the bottle was about 30 mm. A direct current was applied to the iridium wire to obtain a hot wire at 800 ° C. The pressure in the vacuum chamber 6 during film formation was 20 Pa. The film formation time was 15 seconds. A PET bottle coated with the obtained silicon oxide thin film was taken as Example 1. Example 1 was evaluated as follows.

(Evaluation methods)
(1) Oxygen permeability The oxygen permeability of this container was measured under conditions of 23 ° C. and 90% RH using Oxtran 2/20 manufactured by Modern Control, and was measured 72 hours after the start of nitrogen gas replacement. Was described.
(2) Film thickness The film thickness of DLC was measured using DEKTAK3 manufactured by Veeco.
(3) Adhesion The oxide thin film sample formed on the inner surface of the PET bottle was immersed purely at 25 ° C. for 1 week. About the comparatively smooth fixed part among PET bottles, the location which can measure a film thickness was provided using masking, and the film thickness before and behind immersion was measured by the above-mentioned method. Samples having the same film thickness before and after immersion were judged to have adhesion, and samples having a film thickness significantly reduced before and after immersion were judged to have no adhesion.

For Example 1, the oxygen transmission rate was 0.002 cc / container / day. The film thickness was 51 nm. The adhesion was “Yes”. The production conditions and evaluation results are summarized in Table 1.

(Example 2)
The film was formed in the same manner as in Example 1 except that ozone was diluted to 3% with oxygen to obtain a mixed gas, this mixed gas was supplied at 100 sccm, and the sexing film time was 50 seconds. The film forming conditions and results are shown in Table 1.

(Example 3)
Except that the pressure at the time of film formation was 10 Pa, film formation was performed in the same manner as in Example 1 to obtain Example 3. The film forming conditions and results are shown in Table 1.

Example 4
Except that the pressure at the time of film formation was 100 Pa, film formation was performed in the same manner as in Example 1 to obtain Example 4. The film forming conditions and results are shown in Table 1.

(Example 5)
Ozone is diluted to 3% with oxygen to form a mixed gas, this mixed gas is supplied at 100 sccm for 7.5 seconds to form a film, and then ozone is diluted to 10% with oxygen to form a mixed gas. A film was formed by supplying a gas at 100 sccm for 7.5 seconds, and the film was formed in the same manner as in Example 1 except that the oxide thin film was a gradient composition film having a different carbon concentration. The film forming conditions and results are shown in Table 1. This gradient composition film had a carbon concentration of about 5% on the plastic surface, and the carbon concentration was below the detection limit on the surface side of the thin film.

(Example 6)
A film was formed in the same manner as in Example 1 except that hexamethyldisiloxane was used as a non-pyrophoric material, and Example 6 was obtained. The film forming conditions and results are shown in Table 1.

(Example 7)
A film was formed in the same manner as in Example 1 except that phenylsilane was used as a non-pyrophoric material, and Example 7 was obtained. The film forming conditions and results are shown in Table 1.

(Example 8)
A film was formed in the same manner as in Example 1 except that hexamethyldisilazane was used as a non-pyrophoric material, and Example 8 was obtained. The film forming conditions and results are shown in Table 1.

Example 9
Example 9 was carried out in the same manner as in Example 1 except that triisopropoxyaluminum was used as the non-pyrophoric raw material and an aluminum oxide thin film was formed. The film forming conditions and results are shown in Table 1.

(Example 10)
Using the film forming apparatus 100 shown in FIG. 2, the same film was formed on the inner surface of the PET bottle as in Example 1. A molybdenum wire was used as the wire 18, and the non-pyrophoric raw material was molybdenum vapor generated from the molybdenum wire. Ozone was diluted to 10% with oxygen to obtain a mixed gas, and this mixed gas was supplied at 100 sccm. The distance between the wire 18 and the bottom surface inside the bottle was 30 mm. The distance between the wire 18 and the inner side surface of the bottle was about 30 mm. A direct current was applied to the molybdenum wire to obtain an 800 ° C. hot wire. The pressure in the vacuum chamber 6 during film formation was 5 Pa. The film formation time was 30 seconds. A PET bottle coated with the obtained molybdenum oxide thin film was taken as Example 10. About Example 10, evaluation similar to Example 1 was performed. The film forming conditions and results are shown in Table 1. The obtained molybdenum oxide thin film was colored blue.

(Example 11)
Using the film forming apparatus 100 shown in FIG. 2, the same film was formed on the inner surface of the PET bottle as in Example 1. An iridium wire was used as the wire 18, and the non-pyrophoric raw material was an aluminum powder that is a volatile substance supported on the surface of the iridium wire. Ozone was diluted to 10% with oxygen to obtain a mixed gas, and this mixed gas was supplied at 100 sccm. The distance between the wire 18 and the bottom surface inside the bottle was 30 mm. The distance between the wire 18 and the inner side surface of the bottle was about 30 mm. A direct current was applied to the iridium wire to obtain a hot wire at 800 ° C. The pressure in the vacuum chamber 6 during film formation was 5 Pa. The film formation time was 60 seconds. A PET bottle coated with the obtained aluminum oxide thin film was designated as Example 11. About Example 11, the same evaluation as Example 1 was performed. The film forming conditions and results are shown in Table 1.

(Example 12)
Using the film forming apparatus 100 shown in FIG. 2, the same film was formed on the inner surface of the PET bottle as in Example 1. As a non-pyrophoric raw material, 1.5 sccm of trimethylsilane was supplied. Further, a molybdenum wire was used as the wire 18 and molybdenum vapor generated from the molybdenum wire was incorporated into the silicon oxide thin film as an additive component. Ozone was diluted to 20% with nitrogen to obtain a mixed gas, and this mixed gas was supplied at 20 sccm. The distance between the wire 18 and the bottom surface inside the bottle was 30 mm. The distance between the wire 18 and the inner side surface of the bottle was about 30 mm. A direct current was applied to the molybdenum wire to obtain an 800 ° C. hot wire. The pressure in the vacuum chamber 6 during film formation was 10 Pa. The film formation time was 15 seconds. A PET bottle coated with a silicon oxide thin film in which molybdenum was incorporated as an additive component was obtained as Example 12. About Example 12, evaluation similar to Example 1 was performed. The film forming conditions and results are shown in Table 1. The silicon oxide thin film in which molybdenum was incorporated as an additive component was colored blue.

(Comparative Example 1)
Film formation was performed on the outer surface of a round 500 ml PET bottle as the plastic container 11 using the film formation apparatus 200 shown in FIG. The wall thickness of the container wall was about 0.3 mm. An iridium wire was used as the wire 18 and 1.5 sccm of trimethylsilane was supplied as a non-pyrophoric material. Ozone was diluted to 10% with oxygen to obtain a mixed gas, and this mixed gas was supplied at 100 sccm. The distance between the wire 18 and the bottom surface outside the bottle was 55 mm. The distance between the wire 18 and the outer side surface of the bottle was about 55 mm. A direct current was applied to the iridium wire to obtain a hot wire at 800 ° C. The pressure in the vacuum chamber 6 during film formation was 20 Pa. The film formation time was 15 seconds. The obtained PET bottle coated with the silicon oxide thin film was designated as Comparative Example 1. The film forming conditions and results are shown in Table 1. Since the distance between the wire 18 and the bottle surface was as long as 55 mm, the non-pyrophoric raw material and ozone gas were not efficiently in contact with the outer surface of the plastic container after being heated with the hot wire. Therefore, the film forming speed and the film thickness are small, and the gas barrier property cannot be obtained.

(Example 13)
A film was formed in the same manner as in Comparative Example 1 except that the distance between the wire 18 and the outer bottom surface of the bottle was 3 mm, and the distance between the wire 18 and the outer side surface of the bottle was about 3 mm. . The film forming conditions and results are shown in Table 1. Although the gas barrier property was obtained, the distance between the wire 18 and the bottle surface was as short as 3 mm, so that the film formation in the vicinity of the gas blowing hole 17x became excessive and unevenness occurred.

(Comparative Example 2)
A film was formed in the same manner as in Example 1 except that the pressure at the time of film formation was set to 110 Pa. The film forming conditions and results are shown in Table 1. When trimethylsilane was used as the non-pyrophoric raw material, the pressure during film formation was too high, so the non-pyrophoric raw material was granulated before coming into contact with the surface of the plastic container, and the silicon oxide powder in the vacuum chamber Generated. As a result, particle deposition occurred on the bottle surface instead of film formation. The adhesion was “none”.

(Example 14)
Except that the pressure during film formation was set to 8 Pa, film formation was performed in the same manner as in Example 1 to obtain Example 14. The film forming conditions and results are shown in Table 1. When trimethylsilane was used as the non-pyrophoric material, the pressure during film formation was too low, so that the gas barrier property was obtained, but the film formation rate decreased.

(Comparative Example 3)
A film was formed in the same manner as in Example 1 except that 100 sccm of oxygen was supplied instead of ozone, and Comparative Example 3 was obtained. The film forming conditions and results are shown in Table 1. A silicon oxide thin film was not formed.

(Example 15)
A film was formed in the same manner as in Example 1 except that a tungsten wire was used instead of the iridium wire, and Example 15 was obtained. The film forming conditions and results are shown in Table 1. A silicon oxide thin film equivalent to that in Example 1 was formed, but deterioration of the tungsten wire was observed.

(Example 16)
Using the film forming apparatus 100 shown in FIG. 2, the same film was formed on the inner surface of the PET bottle as in Example 1. A tungsten wire was used as the wire 18, and the non-pyrophoric raw material was tungsten vapor generated from the tungsten wire. Ozone was diluted to 10% with oxygen to obtain a mixed gas, and this mixed gas was supplied at 100 sccm. The distance between the wire 18 and the bottom surface inside the bottle was 30 mm. The distance between the wire 18 and the inner side surface of the bottle was about 30 mm. A direct current was applied to the tungsten wire to obtain a hot wire at 2000 ° C. The pressure in the vacuum chamber 6 during film formation was 5 Pa. The film formation time was 30 seconds. A PET bottle coated with the obtained tungsten oxide thin film was designated as Example 16. Example 16 was evaluated in the same manner as in Example 1. The film forming conditions and results are shown in Table 1. The obtained tungsten oxide thin film was formed, but deterioration of the tungsten wire was observed.

(Example 17)
Using the film forming apparatus 100 shown in FIG. 2, the same film was formed on the inner surface of the PET bottle as in Example 1. As a non-pyrophoric raw material, 1.5 sccm of trimethylsilane was supplied. In addition, a tungsten wire was used as the wire 18, and tungsten vapor generated from the tungsten wire was incorporated into the silicon oxide thin film as an additive component. Ozone was diluted to 20% with nitrogen to obtain a mixed gas, and this mixed gas was supplied at 20 sccm. The distance between the wire 18 and the bottom surface inside the bottle was 30 mm. The distance between the wire 18 and the inner side surface of the bottle was about 30 mm. A direct current was applied to the tungsten wire to obtain a hot wire at 2000 ° C. The pressure in the vacuum chamber 6 during film formation was 10 Pa. The film formation time was 15 seconds. A PET bottle coated with a silicon oxide thin film in which tungsten was incorporated as an additive component was obtained as Example 17. About Example 17, the same evaluation as Example 1 was performed. The film forming conditions and results are shown in Table 1. The silicon oxide thin film in which tungsten was incorporated as an additive component had a dark color.

(Comparative Example 4)
An uncoated PET bottle was designated as Comparative Example 4.

  Example 1 was subjected to composition analysis of silicon, carbon, and oxygen in the depth direction by X-ray photoelectron spectroscopy (XPS). The results are shown in FIG. Similarly, Example 2 is shown in FIG. In FIG. 12, no residual carbon was present in the silicon oxide thin film (below the detection limit), but in FIG. 13, 8 atom% of residual carbon remained in the silicon oxide thin film. Therefore, it was found that ozone contributes to reduce residual carbon in the silicon oxide thin film.

  The gas barrier plastic container obtained by the present invention is a plastic container for beverages having gas barrier properties suitable for alcoholic beverages such as beer or soft drinks.

It is a block diagram of the conventional DLC film forming apparatus. It is the schematic which shows one form of the film-forming apparatus which concerns on a 1st form, (a) when a wire is a linear shape, (b) when a wire is a coil spring shape, (c) is a zigzag wire shape. In the case of The other form of the positional relationship of a wire and a source gas supply pipe was shown. It is the schematic which shows one form of the film-forming apparatus which concerns on a 2nd form, (a) is a case where a wire is linear, (b) is a case where a wire is a coil spring shape. An A-A 'cross-sectional view is shown. An A-A 'cross-sectional view is shown. It is a conceptual diagram of the apparatus for depositing a gas barrier thin film simultaneously on the inner surfaces of a plurality of plastic containers. It is a conceptual diagram of the apparatus for forming a gas barrier thin film simultaneously on the outer surface of a plurality of plastic containers. It is a conceptual diagram of the apparatus for depositing a gas barrier thin film simultaneously on the outer surfaces of a plurality of plastic containers in-line. It is a conceptual diagram for demonstrating a container cooling means, (a) is a case where it forms into a film on the inner surface of a plastic container, (b) is a case where it forms into a film on the outer surface of a plastic container. The other form of the thin film formation chamber of FIG. 9 was shown. It is a graph which shows the compositional analysis result of the silicon | silicone in the depth direction by X-ray photoelectron spectroscopy about Example 1, and carbon and oxygen. It is a graph which shows the compositional analysis result of the silicon | silicone in the depth direction by X-ray photoelectron spectroscopy about Example 2, and carbon and oxygen.

Explanation of symbols

1, 12, reaction chamber 1A, carbon source gas inlet 1B, exhaust port 2, external electrode 3, internal electrode 4, high frequency power source 5, 11, plastic container 6, 60, vacuum chamber 8, vacuum valves 13, 63, Lower chamber 14, O-rings 15 and 65, upper chambers 16 and 66, gas supply port 17, source gas flow channels 17 x and 77 x, gas blowing holes 18, wires 19, wiring 20, heater power supply 21, plastic container mouth 22 , Exhaust pipes 23, 73, raw material gas supply pipes 24a, 24b, flow rate regulators 25a, 25b, 25c, valves 26a, 26b, 79a, 79b, connection part 27, cooling water flow path 28, inner surface 29 of the vacuum chamber, cooling means 30, a chamber 31 made of a transparent body, a raw material gas pipe 32, a bottle rotation mechanism 33, 34, a non-pyrophoric raw material and ozone gas 35, and an insulating ceramic Member 36, inner tube 40 made of insulating ceramics with an expansion / contraction mechanism, bottle alignment chamber 41, exhaust chamber 42, thin film formation chamber 43, atmospheric leak chamber 44, take-out chamber 50, cooled liquid or gas 51, container cooling means 100 , 200, deposition equipment

Claims (15)

A step of setting the inside of the vacuum chamber containing the plastic container to a predetermined pressure below atmospheric pressure;
A process of energizing a wire disposed inside the vacuum chamber and generating heat above a predetermined temperature to form a hot wire;
The non-pyrophoric raw material containing silicon or a metal element as a constituent element and ozone gas supplied into the vacuum chamber are heated with the hot wire, and then at least one of the inner surface and the outer surface of the plastic container Contacting one side to form an oxide thin film derived from the non-pyrophoric raw material;
A method for producing a plastic container coated with an oxide thin film, characterized by comprising: The plastic container is carried into the vacuum chamber via a differential pressure mechanism;
The plastic container is transported on the transport path such that the surface of the plastic container approaches a desired distance with respect to the wire installed in the transport path in the vacuum chamber;
The method for producing a plastic container coated with an oxide thin film according to claim 1, further comprising a step of carrying the plastic container out of the vacuum chamber via a differential pressure mechanism.   The method for producing a plastic container coated with an oxide thin film according to claim 1 or 2, wherein, in the step of forming the oxide thin film, the plastic container is irradiated with ultraviolet rays. Using a non-pyrophoric silicified organic compound as the non-pyrophoric raw material and decomposing by a thermal decomposition reaction or catalytic reaction with the hot wire to form a SiO _x thin film as the oxide thin film, or A non-pyrophoric aluminum-containing organic compound is used as the non-pyrophoric raw material, and is decomposed by a thermal decomposition reaction or catalytic reaction with the hot wire to form an AlO _x thin film as the oxide thin film. A method for producing a plastic container coated with the oxide thin film according to claim 1, 2 or 3.   The method for producing a plastic container coated with an oxide thin film according to claim 4, wherein the supply amount of the ozone gas is an amount such that carbon remaining in the oxide thin film becomes substantially zero.   The supply amount of the ozone gas is set to an amount in which carbon remains in the oxide thin film at the start of film formation of the oxide thin film, and then the supply amount is increased so that the carbon remaining in the oxide thin film is substantially increased. 5. The plastic container coated with the oxide thin film according to claim 4, wherein the oxide thin film is a gradient composition thin film having a carbon content different in the thickness direction. Manufacturing method.   The oxidation according to claim 1, 2, 3, 4, 5 or 6, wherein when the hot wire is formed as a hot wire, the wire is formed mainly of a metal or carbon that does not volatilize substantially. A method for producing a plastic container coated with a thin film.   The wire is formed of a metal, a conductive metal compound, or carbon as a main component, and volatilizes carbon, silicon, or a metal element when the hot wire is used, and the carbon, silicon, or metal element is oxidized. The method for producing a plastic container coated with an oxide thin film according to claim 1, wherein the plastic thin film is taken into a physical thin film and becomes an additive component.   The method for producing a plastic container coated with an oxide thin film according to claim 8, wherein the additive component functions as a color center.   The metal element that functions as the color center is cobalt, manganese, copper, iron, chromium, antimony, cadmium, sulfur, selenium, gold, nickel, uranium, vanadium, silver, molybdenum, tin, tungsten, bismuth, or erbium. A method for producing a plastic container coated with the oxide thin film according to claim 9.   The method for producing a plastic container coated with an oxide thin film according to claim 8, wherein the additive component functions as a cross-linking material in the oxide thin film.   12. The method for producing a plastic container coated with an oxide thin film according to claim 11, wherein the additive component functioning as the cross-linking material is sodium, potassium, lithium, lead, carbon, or titanium.   The wire is formed of a metal, a conductive metal compound, or carbon containing at least one component of carbon, silicon, or metal that volatilizes when the hot wire is used, and the hot wire. Vapor containing at least one component of carbon, silicon or metal volatilized from the non-pyrophoric raw material such as non-pyrophoric silicified organic compound or non-pyrophoric aluminum-containing organic compound, The method for producing a plastic container coated with an oxide thin film according to claim 4, wherein the method is a pyrophoric raw material, and the vapor is oxidized to constitute one of the main components of the oxide thin film.   The wire is formed mainly of a metal, a conductive metal compound, or carbon containing at least one component of carbon, silicon, or metal that volatilizes when the hot wire is formed, and the non-natural The ignitable raw material is a vapor containing at least one component of carbon, silicon or metal volatilized from the hot wire, and the oxide thin film is an oxide thin film obtained by oxidizing the vapor. The manufacturing method of the plastic container which coat | covered the oxide thin film of Claim 1, 2, or 3.   The vapor is molybdenum, copper, aluminum, palladium, tungsten, silver, silicon, carbon, sodium, potassium, lithium, lead or titanium or a compound containing these, and the oxide thin film is molybdenum, copper, aluminum, 15. The method for producing a plastic container coated with an oxide thin film according to claim 14, wherein an oxide of palladium, tungsten, silver or silicon is a main component.