WO2008062730A1 - Process for producing plastic container coated with oxide thin film - Google Patents

Abstract

An inexpensive process for producing a plastic container coated with a gas barrier thin film, in which a thin film with gas barrier property can be formed safely at high speed from low-cost raw materials, and in which use can be made of a production apparatus not requiring any expensive equipment. The process comprises the steps of adjusting the interior of vacuum chamber (6) accommodating plastic container (11) to a given pressure equal to atmospheric pressure or below; passing electric current through wire (18) disposed inside the vacuum chamber to thereby attain heating to a given temperature or higher so that the wire is converted to a hot wire; and heating by means of the hot wire ozone gas and a nonpyrophoric raw material containing silicon or a metal element as a constituent element, fed into the interior of the vacuum chamber and thereafter effecting contact with at least either the internal surface or the external surface of the plastic container to thereby form an oxide thin film derived from the nonpyrophoric raw material.

Description

 Specification

 Method for producing plastic container coated with oxide thin film

 Technical field

 [0001] The present invention includes, as contents, for example, alcoholic beverages such as beer that dislike oxidation from the standpoint of quality and require no escape of carbon dioxide from the container wall, or soft drinks that similarly dislike oxidation. More particularly, the present invention relates to a beverage plastic container having a barrier property against oxygen gas and carbon dioxide gas. 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. It relates to a method of manufacturing plastic containers with excellent recyclability. In addition to gas barrier properties, it has the above-mentioned advantages for covering oxide thin films that are functional in terms of color, glossy and translucent / light-shielding properties, cosmetics, and distinguishability relatively easily and at low cost. The present invention relates to a method for manufacturing a plastic container. Background art

 In recent years, a DLC (Diamond Like Carbon) film has been put to practical use as a single-layer thin film coated on a PET bottle. This DLC film is a film having an amorphous three-dimensional structure composed of carbon atoms and hydrogen atoms, and is a hard carbon film having a hard and excellent insulating property, a high refractive index, and a very smooth morphology.

 Conventionally, there is an example in which such a DLC film formation 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. After the carbon source gas is introduced from the introduction port 1A, a high frequency power is applied between the internal electrode 3 and the external electrode 2 from the high frequency power source 4 to excite the carbon source gas, thereby generating a plastic container 5 A DLC film is formed on the inner surface.

[0004] In addition, there is a technique for forming a silicon oxide thin film (SiOx) in a small plastic container instead of the 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. In addition, 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 formation 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).

 [0006] Patent Document 1: Japanese Patent No. 2788412

 Patent Document 2: Japanese Utility Model Publication No. 5-35660

 Patent Document 3: Japanese Patent Application Laid-Open No. 2004-217966 (Paragraph 0004, Paragraph 0022)

 Disclosure of the invention

 Problems to be solved by the invention

 However, since the plasma CVD film forming apparatus uses relatively expensive equipment, it is not always possible to manufacture a plastic container having a gas barrier property at a low price.

 [0008] Since the catalytic chemical vapor deposition method does not require the use of expensive equipment such as a high-frequency power source, the cost of the device itself is less than the cost of the plasma CVD film forming device.

 However, when forming a silicon oxide thin film, for example, by catalytic chemical vapor deposition, according to the study of the present inventors, when methylsilane, dimethylsilane, or trimethylsilane is used as a source gas, the reaction is performed in an oxygen atmosphere. Even in such a case, it was not possible to cause a sufficient oxidation reaction, and it was not possible to form a silicon oxide thin film in close contact with the plastic substrate. On the other hand, if hydrogen hydride such as monosilane, disilane, or trisilane is used as the source gas, the cost of a safety device with high explosiveness and danger represented by pyrophoric properties is increased, and the plasma CVD film forming apparatus is used. On the other hand, the cost merit is diminished. Furthermore, when forming a silicon oxide thin film, it is necessary to supply the source gas and the oxidizing gas together. However, if tungsten wire is used as the thermal catalyst (Patent Document 3, paragraph 0059), tungsten is oxidized. There is a problem of being deteriorated.

 [0010] 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.

[0011] Here, the present invention is mainly directed to plastic containers for beverages and foods. In this area, there are significant cost constraints on products associated with handling beverages and food. It also features the use of highly safe methods and materials for the production process and product containers. Therefore, the use of pyrophoric raw materials represented by the above silanes and alkylaluminums is not practical from the viewpoint 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, in this field, raw materials containing halogens are generally avoided and are not practical from the viewpoint of the present invention.

Therefore, an object of the present invention is to provide a non-naturally-occurring container having a three-dimensional shape made of plastic at room temperature in a method for producing a gas-barrier thin film-coated plastic container that does not rely on these non-practical raw materials. Using an ignitable raw material and ozone, it is possible to form a thin film with gas barrier properties at a low temperature safely and at high speed, and an inexpensive manufacturing method that can be operated in a manufacturing apparatus that does not require expensive equipment. Is to provide.

[0013] In addition, containers in the beverage / food field are required to have translucency / light-shielding properties and coloration in order to protect the contents, visually check the quality, and improve the appearance. In response to these problems, practical translucent / light-shielding properties and coloration without directly coloring the resin can be controlled easily with a relatively high degree of freedom. It is also an object of the present invention to provide a manufacturing method to be applied to the container.

 Means for solving the problem

[0014] The present inventor has intensively developed to solve the above-mentioned problems. As a result, the wire is heated and energized, and a highly safe and non-pyrophoric raw material is heated together with ozone gas with this hot wire. As a result, it was found that an oxide having a gas barrier property derived from a non-pyrophoric raw material can be formed with good adhesion, and the present invention was completed.

[0015] Here, in the present invention, a wire means an object that can heat an electric resistor by energization to several hundred degrees or more using a general industrial power source. Typically, it is a metal wire, but a conductive metal compound or a carbon rod-like body is also included in this concept. Furthermore, an object having a carrier '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 heat load applied to each part of the container surface against a complicated three-dimensional shape 'resistance heating so that the flow of the film forming substance is suitable for film formation. It is because it is common in the point which can arrange a body. Relatedly, in the present invention, the hot wire means a wire that is resistance-heated by energization.

 [0016] Specifically, the method for producing 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, A process of energizing a wire disposed inside to generate heat above a predetermined temperature to form a hot wire, and a non-pyrophoric material containing a key element or metal element supplied as a constituent element to the inside of the vacuum chamber Heating the raw material and ozone gas with the hot wire, and then bringing the raw material and ozone gas into contact with at least one of the inner surface and the outer surface of the plastic container to form an oxide thin film derived from the non-pyrophoric raw material; It is characterized by having.

 [0017] In the method for producing a plastic container coated with an oxide thin film according to the present invention, the plastic container includes a step of bringing the plastic container into the vacuum chamber via a differential pressure mechanism, and the plastic container includes the A step of transporting the plastic container so that the surface of the plastic container approaches a desired distance from the wire installed in the transport path in the vacuum chamber; and the plastic container is disposed outside the vacuum chamber. And a step of unloading via a differential pressure mechanism. It is also possible to mass-produce plastic containers coated with oxide thin films.

 [0018] 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 inside of the vacuum chamber is The pressure is preferably 10 to 100 Pa. In addition to preventing particle formation in the gas phase due to decomposition of non-pyrophoric raw materials, an oxide thin film can be formed at high speed on the surface of a plastic container.

In the method for producing a plastic container coated with an oxide thin film according to the present invention, it is preferable to irradiate the plastic container with ultraviolet rays in the step of forming the oxide thin film. The surface of the plastic container can be sterilized. In addition, UV irradiation promotes the decomposition of ozone to increase the oxidizing power and promotes the oxidation of non-pyrophoric raw materials. At this time, the non-pyrophoric raw material and ozone gas are heated by the hot wire. The reaction can proceed.

[0020] In the method for producing a plastic container coated with an oxide thin film according to the present invention, a non-pyrophoric key organic compound is used as the non-self-igniting raw material, It is decomposed by catalytic reaction to form a SiO thin film as the oxide thin film, or a non-pyrophoric aluminum-containing organic compound is used as the non-pyrophoric raw material, and a thermal decomposition reaction is performed with the hot wire. Alternatively, it is preferable that an AIO thin film is formed as the oxide thin film by being decomposed by a catalytic reaction. Unlike pyrophoric raw materials such as non-pyrophoric key organic compounds or non-pyrophoric aluminum-containing organic compounds such as silane-based materials or trimethylaluminum, there is no need to spend on safety equipment. As a result, it is inexpensive. Furthermore, even if these non-pyrophoric materials are supplied simultaneously with oxygen and heated with a hot wire, an adherent SiO thin film or AIO thin film is not formed on the plastic substrate. As in the present invention, a non-pyrophoric raw material and ozone gas are simultaneously supplied and heated with a hot wire, and then thermal decomposition and oxidation are sufficiently advanced to form a SiO thin film or an AIO thin film with good adhesion to the substrate. The

 [0021] 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 an amount such that carbon remaining in the oxide thin film is substantially zero. Is preferred. 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.

 [0022] And, when the carbon remaining in the oxide thin film is substantially zero, the gas nooricity becomes 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.

[0023] 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 set so that carbon remains in the oxide thin film when the oxide thin film is formed. The amount of carbon remaining in the oxide thin film is set so that the amount of carbon remaining in the oxide thin film becomes substantially zero after that, and the carbon content of the oxide thin film differs in the thickness direction. It is preferable to use a gradient composition thin film. If the supply amount of ozone gas is small! /, And carbon remains in the oxide thin film and the supply amount is sufficient or more, the oxide thin film No carbon remains in the film. If carbon remains in the oxide thin film, the adhesion to the substrate becomes strong. On the other hand, if the carbon remaining in the oxide thin film is substantially zero, the gas barrier property is the best. Therefore, carbon is left in the oxide thin film on the substrate surface side, and a gradient composition film is formed so that no carbon remains on the surface side of the oxide thin film, thereby providing excellent adhesion to the substrate and gas barrier properties. Can be a good oxide thin film.

 [0024] In the method for producing a plastic container coated with an oxide thin film according to the present invention, the wire 1 is formed mainly of a metal or carbon that does not substantially volatilize when the hot wire is used. It is preferable to become. Regardless of the composition of the wire, a non-pyrophoric raw material is thermally decomposed to obtain an oxidized oxide thin film.

 [0025] In the method of manufacturing a plastic container coated with an oxide thin film according to the present invention, the wire is formed mainly of a metal, a conductive metal compound, or carbon, and carbon when used as the hot wire. It is preferable that volatilization of the key element or metal element and the addition of the carbon, key element or metal element into the oxide thin film become 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.

 [0026] 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 calorie component functions as a color center can be selected. Applying color to oxide thin film.

 [0027] 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, force donium, sulfur, Examples include selenium, gold, nickel, uranium, vanadium, silver, molybdenum, tin, tungsten, bismuth or erbium.

 [0028] In the method for producing a plastic container coated with an oxide thin film according to the present invention, it is possible to select an embodiment in which the additive calorie component functions as a cross-linking material in the oxide thin film. This is because the physicochemical stability of the oxide thin film can be improved or the refractive index can be adjusted.

[0029] In the method for producing a plastic container coated with an oxide thin film according to the present invention, the additive component that functions as the cross-linking material is sodium, potassium, lithium, lead, carbon, or titanium. Is included.

 [0030] In the method of 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. Therefore, it is possible to select an aspect that is taken into the oxide thin film and becomes an additive component. 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.

 [0031] In the method for producing a plastic container coated with an oxide thin film according to the present invention, the wire 1 contains at least one component of carbon, silicon, or metal that volatilizes when the hot wire is used. A vapor containing at least one of carbon, silicon, or metal volatilized from the hot wire and formed of a metal, a conductive metal compound, or carbon as a main component. Together with the non-pyrophoric raw material such as a pyrophoric key organic compound or a non-pyrophoric aluminum-containing organic compound, it becomes a non-pyrophoric raw material, and the vapor is oxidized to become one of the main components of the oxide thin film. 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 flame is also a main component.

 [0032] In the method for producing a plastic container coated with an oxide thin film according to the present invention, the wire contains at least one component of carbon, silicon, or metal that volatilizes when the hot wire is used. And the non-pyrophoric raw material is composed of at least one component of carbon, carbon or metal volatilized from the hot wire. It is possible to select an embodiment in which the vapor is an oxide thin film in which the vapor is oxidized. This is because an oxide thin film whose main component is a wire-derived component can be formed. If the steam is derived from wire, the safety will be further improved and the raw material introduction means will be simplified. Further, the composition of the thin film can be easily controlled by adjusting the composition of the wire.

[0033] According to the present invention, in the manufacturing method of the plastics container of the oxide thin film above the wire component is added to the coating, the steam is saturated steam pressure 10- ⁴ Pa or more below 2000 ° C Preferably, it is a vapor of a simple substance of a metal or 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. [0034] In the method for producing a plastic container coated with the oxide thin film according to the present invention, the vapor, molybdenum, copper, aluminum, palladium, tungsten, silver, silicon, carbon, sodium, potassium, lithium, lead or It is preferable that the oxide thin film is titanium or a compound containing these, and the oxide thin film is mainly composed of an oxide of molybdenum, copper, aluminum, palladium, tungsten, silver, or silicon. Oxide thin films with different colors depending on the metal species are obtained. In addition to the main component steam (molybdenum, copper, aluminum, palladium, tandastene, silver or silicon-containing steam), these additional vapors (sodium, potassium, lithium, carbon, lead) Alternatively, steam containing titanium) may be added.

 [0035] 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 the oxide 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 volatilizes and the volatilization occurs. In addition to the vapor from which the volatile substance has volatilized from the wire, the non-pyrophoric raw material can be selected as a main component of the oxide thin film. This is because it is possible to form 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 added component. In addition, it is possible to form an oxide thin film in which a component derived from one wire is a main component and a component derived from a volatile substance carried on the wire is also a main component.

 [0036] In the method for producing a plastic container coated with an oxide thin film according to the present invention, the non-self-igniting raw material is a volatile substance applied or supported on the surface of the wire, In this case, it is possible to select a mode in which the volatile substance volatilizes and becomes the main component of the oxide thin film. This is because an oxide thin film whose main component is a component derived from a volatile substance can be formed. If it is derived from volatile substances, the safety will be high and the raw material introduction means will be simplified.

[0037] In the method for producing a plastic container coated with an oxide thin film according to the present invention, the volatile substance is molybdenum, copper, aluminum, palladium, tungsten, silver, or a compound containing these. Is preferred! Oxide thin films with different colors depending on the metal species can be obtained. The invention's effect

 According to the present invention, in a method for producing a gas-noria 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. It is possible to form a thin film having a low temperature. This manufacturing method is an inexpensive manufacturing method that can be operated with manufacturing equipment that does not require expensive equipment.

[[FIG. 11]] It is a configuration diagram of a conventional DDLLCC film forming apparatus. .

 [[FIG. 22] FIG. 22 is a schematic schematic diagram showing one form of the film deposition apparatus apparatus according to the eleventh form, and ((aa )) Is when the wire is in the shape of a straight line, ((bb)) is when the wire is in the shape of a spring if it is cocoyl, and ((cc)) is If the wire has a zigzag line shape, then .

 [[Fig. 33]] Another form of the positional relationship between the wireless wire and the raw material feed gas supply pipe is shown. .

[[FIG. 44]] FIG. 44 is a schematic schematic diagram showing one form of the film deposition apparatus according to the twenty-second form, and ((aa )) Is when the wire is linear, and ((bb)) is when the wire is of a spring-like shape. .

[[Fig. 55]] A cross-sectional view of ΑΑ--ΑΑ '' is shown. .

[[Fig. 66]] ΑΑ--ΑΑ '' Cross section view is shown. .

 [[Fig. 77]] A thin gas film of Gagasubaria is formed on the inner surface of the plurality of plastic plastic containers at the same time. FIG. 2 is a schematic conceptual diagram of a device for sulling and laying down. .

 [[Fig. 88]] Form a thin film of Gagasubaria rear thin film on the outer and outer surface surfaces of multiple plastic plastic containers at the same time. FIG. 2 is a schematic conceptual diagram of an apparatus for laying down. .

 [[Fig. 99]] A thin gas film of Gagasubaria rear is simultaneously applied to the outer and outer surface surfaces of multiple plastic plastic containers. FIG. 2 is a schematic conceptual diagram of a device for depositing a film. .

 [[Figure 1100]] A schematic conceptual diagram for explaining the container cooling / cooling means, ((aa)) is When depositing a film on the inner surface of the container, ((bb)) is on the outer surface of the polypropylene container. In the case of depositing a film on a film, .

[[FIG. 1111]] Another form of the thin film film forming chamber shown in FIG. 99 is shown. .

[[FIG. 1122]] In the actual working example 11, according to the XX-ray photoelectron spectroscopy spectrophotometry, the key element in the direction of depth, , Carbon and carbon and acid

[[FIG. 1133]] According to Example 22 of actual implementation, the key element in the direction of depth according to the XX-ray photoelectron spectroscopy method, , Carbon and carbon and acid It is a graph which shows a compositional analysis result of an element. 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 supply

 5, 11, plastic container

 6, 60, vacuum chamber

 8, vacuum valve

 13, 63, lower chamber

 14, 〇 ring

 15, 65, upper channo

 16, 66, gas supply port

 17, Raw material gas flow path

 17x, 77x, gas blower

 18, wire

19, wiring

 0, heater power

 1, mouth of plastic container

 2, exhaust pipe

 3, 73, Raw material gas supply pipe

 4a, 24b, flow regulator

 5a, 25b, 25c, / ku / ref, '

 6a, 26b, 79a, 79b, connection

 7, cooling water flow path

8, inner surface of vacuum chamber 29, cooling means

 30, Transparent chamber

 31, Raw material gas piping

 32, bottle rotation mechanism

 33, 34, Non-pyrophoric raw materials and ozone gas

 35, Insulating ceramic material

 36, Insulating ceramics inner tube with expansion and contraction mechanism

 40, Bottle alignment room

 41, exhaust chamber

 42, Thin film formation chamber

 43, air leak chamber

 44, take-out room

 50, cooled liquid or gas

 51, container cooling means

 100, 200, deposition system

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0041] 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 describing a method for manufacturing a plastic container coated with an oxide thin film according to the present 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 common site | part components.

 [0042] (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. FIG. 2 is a schematic diagram showing the film forming apparatus according to the first embodiment, where (a) is a wire having a linear shape, (b) is a wire having a coil spring shape, and (c) is a zigzag wire. In the case of a line shape. However, FIGS. 2 (b) and 2 (c) are partially enlarged views of the source gas supply pipe 23. FIG. Unless otherwise specified, “FIG. 2” will be described as “FIG. 2 (a)”. The film forming apparatus 100 shown in FIG. 2 includes a vacuum chamber 6 that accommodates a plastic container 11 and a vacuum chamber 6. An evacuation pump (not shown) that evacuates the inside of the plastic container 11 is detachably disposed, and supplies a raw material gas (non-pyrophoric raw material) and ozone gas into the plastic container 11. A raw material gas supply pipe 23 formed of the above material, 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.

[0044] 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 in order to prevent reflection of light emitted as the wire 18 generates heat. (Rmax) O. It preferably has irregularities of 5 m or more. The surface roughness (Rmax) is measured using, for example, a surface roughness measuring device (DEKTAK3 manufactured by ULVAC TECHNO CORPORATION). In order to make the inner surface 28 a black inner wall, there are methods of plating treatment such as black nickel plating and black chrome plating, chemical film treatment such as Raydent's black dyeing, or applying black paint and coloring. Further, it is preferable to provide a cooling means 29 such as a cooling pipe through which the cooling water flows inside the vacuum channel 6 (not shown) or outside (FIG. 2) 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 light reflection and cooling the vacuum chamber 6, the temperature rise of the plastic container 11 and the accompanying thermal deformation can be suppressed. Further, if 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 placed inside the lower chamber 13, the temperature of the glass chamber in contact with the plastic container 11 rises. Difficult to plastic The thermal effect on the 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 raw material gas supply pipe 23, for example, there is a double pipe structure. In the source gas supply pipe 23, the inner pipe 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. The blowout hole is 17x. As a result, the raw material gas and the ozone gas are blown out from the gas blowing hole 17x 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 raw material gas supply pipe 23, and serves 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, 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 the cooling water is folded back and returned here. The entire raw material gas supply pipe 23 is cooled by the cooling water passage 27. Cooling can reduce the thermal effect on the plastic container 11. 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 composed of aluminum nitride, silicon carbide, silicon nitride, or aluminum oxide, or a material mainly composed of aluminum nitride, silicon carbide, silicon nitride, or aluminum oxide. A metal tube whose surface is coated is preferable. The wire can be stably energized, durable, and the heat generated by the wire can be heated by heat conduction.

The raw material 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 and 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 It is formed by a dense tube, and the cooling water flows as a cooling water flow path. The wire is the force S that is routed along the side wall of the source gas supply pipe, and the source gas and ozone that have passed through the hole provided in the side wall of the outer pipe are in contact with the wire in the portion along the side wall, and the pyrolyzed source material is It can be oxidized efficiently.

 [0047] If the gas blowing hole 17x 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 a force S so that the distance L1 from the gas blowing hole 17x to the bottom of the plastic container 11 is 5 to 50 mm. It is more preferable than forming force S to be 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 greater than 50 mm, it will be difficult to form a thin film on the bottom of the plastic container 11, and if the distance is less than 5 mm, it will be difficult to blow out the source gas, or the gas blowing holes on the inner surface of the plastic container 11 Film formation near 17x tends to be excessive.

[0048] The wire 18 is heated by energization to form a hot wire, thereby thermally decomposing the non-pyrophoric raw material and the ozone gas. Oxidation of non-pyrophoric raw materials is promoted by the pyrolyzed ozone, and an oxide thin film is formed on the inner surface of the plastic container 11. In the present 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, or an Ir-based alloy wire, Re Base alloy wire, Pt base wire or Au base wire. The wire 18 may be a carbon-based object such as carbon fiber. Since it has conductivity, it becomes possible to generate heat by energization. The wire 18 is not only a hot wire as a heating means, but may also be a thermal catalyst by a catalytic chemical vapor deposition method. However, tungsten wire, which is normally used as a thermal catalyst for catalytic chemical vapor deposition, should be avoided in an atmosphere containing ozone gas because it deteriorates when oxidized. The wire 18 is formed in a wiring shape, and one end of the wire 18 is connected to a connection portion 26a that is a connection portion between the wiring 19 and the wire 18 provided below the fixed portion in the upper chamber 15 of the source gas supply pipe 23. The And it is supported by the insulating ceramic member 35 provided in the gas blowing hole 17x which is the tip portion. Further, the other end of the wire 18 is connected to the connecting portion 26b by folding. Thus, the wire 18 is the source gas Since it is supported along the side surface of the supply pipe 23, the supply pipe 23 is arranged so as to be positioned substantially on the main axis of the internal space of the lower chamber 13. In FIG. 2 (a), the wire 18 is shown arranged around the source gas supply pipe 23 so as to be parallel to the axis of the source gas supply pipe 23. As a result, it is possible to wrap around the side surface of the source gas supply pipe 23 in a spiral shape, support it with the insulating ceramics 35 fixed in the vicinity of the gas blowing hole 17x, and then fold it 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. FIG. 2 (a) shows 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. 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 to arrange the wire 18 slightly away from the side surface of the raw material gas supply pipe 23! /. This is to prevent a rapid temperature rise of the raw material gas supply pipe 23. Further, it is possible to increase the chances of contact with the non-pyrophoric raw material and ozone gas blown from the gas blowing hole 17x and the non-pyrophoric raw material and ozone gas in the reaction chamber 12. 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 raw material gas supply pipe 23 including the wire 18 is inserted through the opening 21 of the plastic container. Therefore, if the wire 18 is separated from the surface of the raw material gas supply pipe 23 more than necessary, the raw material gas supply pipe 23 is easily contacted when inserted from the mouth portion 21 of the plastic container. The 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 the positional deviation when inserting from the mouth part 21 of the plastic container. Here, the inner diameter of the mouth 21 is approximately 21 · 7−39.8 mm.

It is preferable that the upper limit temperature when the wire 18 is heated is not higher than the temperature at which the wire softens. The operating temperature of the hot wire varies depending on the material of the wire. If Ir, the force that can raise the temperature to the softening temperature is 300 to 1800 ° C, for example, S preferably 800 to 1100 ° C It is more preferable that In addition, by supplying ozone gas together with non-pyrophoric raw materials, the reaction at a low temperature of 300 ° C. is possible as described above even with the hot wire method instead of the catalytic chemical vapor deposition method. Generally, wire If one and the substrate are heated to some extent, the film quality tends to be better. However, the plastic substrate cannot be subjected to much heat load so as not to be thermally deformed. In this respect, if it is 800-1100 ° C, problems caused by heat load from the wire will occur for several hundred seconds or more compared to containers made of plastic materials such as PET resin, which are common in the beverage and food fields. This is the preferred setting.

 [0050] Further, the wire 18 has a portion obtained by processing a wire into a coil spring shape as shown in Fig. 2 (b) in order to increase the chance of contact with the non-pyrophoric raw material and ozone gas. It is preferable. The coil spring shape includes not only a cylindrical shape but also a conical shape, a barrel shape or a zigzag shape, and an unequal pitch shape in which the pitch between these windings is changed. In addition, as shown in Fig. 2 (c), it has a part processed into a zigzag line shape! Or! / Has a part of wire rod processed into a wavy line shape! /, But it is good (not shown). Even in these! /, Misalignment forms, the wire 18 is preferably disposed along the blowing direction of the non-pyrophoric raw material and ozone gas. This increases the chance that non-pyrophoric raw materials and ozone gas 33 will come into contact with wire 18.

 [0051] The method of fixing the source gas supply pipe 23 of the wire 18 may be 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 channel. A wire may be wound directly around the porous outer tube. In addition to improving the stability of fixing the wire, the non-pyrophoric raw material and ozone gas are also 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 raw material 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 chances of non-pyrophoric raw materials and ozone gas 33 coming into contact with 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 18a and 18b It is preferable that the portions are arranged to face different directions. In Fig. 3, the wires are in a vertical and horizontal relationship. The shape of the cross section of the source gas supply pipe 23 is a square in FIG. 3, but may be a circle, an ellipse or a rectangle. In addition, if the tube diameter is inserted through 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 part. 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.

[0053] A heater power supply 20 is connected to the wire 18 via connection portions 26a and 26b and a wiring 19. By causing electricity to flow through the wire 18 by the heater power source 20, the wire 18 generates heat.

 [0054] Further, since the draw ratio at the time of forming the plastic container 11 is small from the mouth portion 21 of the plastic container to the shoulder of the container, if the wire 18 that generates heat at a high temperature is placed nearby, the plastic container 11 is deformed by heat. Cheap. According to the experiment, the shoulder force of the plastic container 11 is heated unless it is separated from the lower end of the plastic container mouth 21 by the positional force S of the connection parts 26a and 26b, which is the connection point between the wiring 19 and the wire 18. Deformation occurred, and when separated beyond 50 mm, a thin film formed on the shoulder of the plastic container 11. Therefore, the wire 18 is preferably arranged so that its upper end is located 5 to 50 mm below the lower end of the mouth 21 of the plastic container. That is, it is preferable that the distance L2 between the connecting portions 26a, 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.

 Further, an exhaust pipe 22 is communicated 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). It has become.

 [0056] (Second form: film formation on the outer surface of the container)

Next, a film forming apparatus according to the second embodiment capable of forming a gas barrier thin film on the outer surface of the container will be described. 4A and 4B are schematic views showing one 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 a schematic diagram of the wire. Unless otherwise specified, “Fig. 4” will be explained as “Fig. 4 (a)”. The film deposition apparatus 200 shown in FIG. 4 includes a vacuum chamber 60 that accommodates the plastic container 11, an exhaust pump (not shown) that evacuates the vacuum chamber 60, and a plastic container. Heat is generated by energizing the wire 18 disposed around the vessel 11, the raw gas pipe 31 for supplying the non-pyrophoric raw material and the ozone gas to the space outside the plastic container 11 in the vacuum chamber 60, and the wire 18. And a heater power source 20 to be operated. In the film forming apparatus 200, the opening of the plastic container 11 is fixed by the bottle rotation mechanism 32, and the plastic container 11 is arranged so that the bottom does not contact inside the vacuum chamber 60! /

 [0057] 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 which is detachably attached to the upper portion of the lower chamber 63 and seals the inside of the lower chamber 63 with an 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 inner 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 at one end thereof to a connecting portion 79a which is a connecting portion between the wiring 19 and the wire 18. 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. Then, 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, FIG. 5 shows an AA ′ cross-sectional view. The wire 18 and the plastic container 11 are equally spaced on the left and right sides in the figure. The wire 18 is arranged so that the distance from the outer surface of the plastic container 11 is constant! The film thickness uniformity 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, a plurality of wires 18 are arranged at rotationally symmetric positions with respect to the main axis of the plastic container! 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 AA ′. 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, the uniformity of film formation can be improved by forming the plastic container 11 while rotating the plastic container 11 around the main axis by the bottle rotating mechanism 32. In particular, in the case of FIG. 5, since the wire 18 is a pair, 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 spirally wound form around the plastic container 11 around the main axis of the plastic container 11, or a plurality of cross sections of the main axis of the plastic container 11 Above, 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 rotating mechanism 32. Here, when a plurality of sets of wires 18 are arranged, it is preferable that the wires 18 be arranged at a distance of 5 cm or more. It promotes the oxidation of non-pyrophoric raw materials without causing thermal damage to the plastic container, making it easy to obtain a uniform film thickness. The material of the wire 18 may be the same as that of the first form.

 [0059] In order to increase the chance of contact with the non-pyrophoric raw material and ozone gas, the wire 18 preferably has a portion obtained by processing a wire into a coil spring shape as shown in Fig. 4 (b). That's right. The coil spring shape includes not only a cylindrical shape but also a conical shape, a barrel shape, or a stitch shape, and 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 rod 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 are given a vector component in the non-pyrophoric raw material and ozone gas blowing direction. This increases the chances of non-pyrophoric raw materials and ozone gas coming into contact with the wire.

[0060] 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, and a gas blowing hole 77x is provided at the tip of each. 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 regulators 24a to 24b, and the valves 25a to 25c. This makes it non-pyrophoric The raw material and ozone gas 33 are blown out from the gas blowing holes 77χ. The gas blowing holes 77χ are all directed to the outer surface of the plastic container 11, and it is possible to spray the non-pyrophoric raw material and ozone gas on the outer surface! A wire 18 is disposed on the outlet side of the gas blowing hole 77χ. As a result, the contact between the wire 18 and the non-pyrophoric raw material and ozone gas often occurs, so that the oxidation of the non-pyrophoric raw material can be promoted.

 [0061] 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. Further, the same ceramic tube as in the first embodiment or a metal tube whose surface is coated with a ceramic material may be used.

 [0062] The length of the source gas supply pipe 73 is preferably formed such that the distance L3 from the gas blowing hole 77χ 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. If the distance is larger than 50 mm, a thin film is formed on the outer surface of the plastic container 11, and if the distance is smaller than 5 mm, the raw material gas can be blown out.

 [0063] 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, it is possible to blow out the pyrolyzed non-pyrophoric raw material from the raw gas supply pipe. Since the wire is arranged 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.

 [0064] In order to prevent thermal deformation of the plastic container 11, a cooling means 29 such as a cooling pipe through which cooling water flows is provided inside or outside the vacuum chamber 60 to prevent the temperature of the lower chamber 63 from rising. preferable.

[0065] A heater power source 20 is connected to the wire 18 via connection portions 79a and 79b 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 embodiment, the working temperature of the wire 18 is preferably 300 to 1800 ° C. 8 00 ~; 1100 ° C is more preferred! /

[0066] Further, an exhaust pipe 22 is communicated 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). It has become. Although not shown, in both the first and second embodiments, the ozone gas silently discharges, for example, oxygen gas from an oxygen cylinder using a commercially available relatively inexpensive ozone generator. It can be obtained from a gas cylinder (manufactured by Iwatani Corporation) that contains ozone gas stably!

[0067] 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 the non-pyrophoric raw material thermally decomposed by ozone can be oxidized. If a set is prepared, an oxide thin film can be formed in a large amount of plastic containers at once. 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 oxidize them. 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 wires 18 are arranged so as to surround each plastic container 1 1 and non-pyrophoric from the source gas supply pipe 73. The raw material and ozone gas are brought into contact with the wire 18 and then sprayed onto the plastic container 11. Here, the mouth is fixed to the bottle rotating mechanism 32, and a thin film is formed on the outer surface of the plastic container 11 while rotating. Further, 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 formation chamber 42 is kept at a constant pressure by the pressure difference mechanism. The exhaust chamber 41 and the air 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. When the plastic container passes through the transfer path in the vacuum chamber, The desired distance between the wire 18 and the surface of the plastic container, for example, 5 to 50 mm is approached. 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 regardless of the shape of the container, and no high frequency power source is required. A film can be formed on the container. This makes the apparatus less expensive than a film forming apparatus using a high-frequency power source.

 [0068] In any of the film forming apparatuses of the first and second embodiments, since the non-pyrophoric raw material and the ozone gas 33 become hot air, the plastic container 11 is likely to be thermally deformed, and therefore a container cooling means is provided. It is preferable. 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. 10 (a), the non-pyrophoric raw material, which is hot air, and 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 for applying the liquid or gas 50. The container cooling means 51 is a water tank when the plastic container 11 is immersed in a liquid such as water, and a shower when the plastic container 11 is showered with a liquid such as water. In addition, when a gas such as cooling nitrogen gas or cooling carbon dioxide gas is blown into the plastic container 11, it is a blower. Cooled nitrogen gas can be easily obtained by using liquid nitrogen and cooled carbon dioxide gas by using dry ice. As shown in FIG. 10 (b), 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, and the second embodiment of the film forming apparatus is an inner surface of the plastic container 11. In addition, it is preferable to have container cooling means 51 for applying the cooled liquid or gas 50 thereto. The container cooling means 51 is a liquid filling device when filling a plastic container 11 into a liquid such as water, and when blowing a gas such as cooling nitrogen gas or cooling carbon dioxide gas to the inner surface of the plastic container 11. One blower.

FIG. 11 shows another embodiment of the thin film forming chamber 42 shown in FIG. On the side wall of the thin film deposition chamber 42, the raw material gas supply pipes 23 and the container cooling means 51 are alternately arranged along the moving direction of the plastic container 11. Plastic container 11 is moved by conveyor (conveyance path, not shown) It is made to rotate. 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 conveyer, 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 cooled by the container cooling means 51. These are performed alternately. At this time, thin film formation proceeds.

 [0070] Next, a method for producing a plastic container coated with an oxide thin film according to this embodiment will be described. If the film forming apparatus 100 in FIG. 2 is used, an oxide thin film can be coated on the inner surface of the plastic container. On the other hand, if the film forming apparatus 200 in FIG. 4 is used, the oxide thin film is applied to the outside of the plastic container. It is possible to coat the surface. Since these two film forming methods have the same process, unless otherwise specified, a film forming apparatus 100 shown in FIG. 2 is used as a representative example to form an oxide thin film on the inner surface of a plastic container. The membrane method will be described. Note that an oxide thin film can be formed on both the inner and outer surfaces of a plastic container using the film forming apparatus 100 and the film forming apparatus 200.

 [0071] The method for producing a plastic container coated with an oxide thin film according to the present embodiment is a process of setting the inside of the vacuum chamber 6 containing the plastic container 11 to a predetermined pressure of atmospheric pressure or less (hereinafter referred to as a decompression process). And a process of supplying heat to a wire 18 disposed inside the vacuum chamber 6 to generate heat above a predetermined temperature to form a hot wire (hereinafter referred to as a hot wire process), and supplying to the inside of the vacuum chamber 6 In addition, non-pyrophoric raw material containing ozone or metal element as constituent element and ozone gas 33 are heated by hot wire 18 and then brought into contact with the inner surface of plastic container 11 to make non-pyrophoric raw material. Forming an oxide thin film derived therefrom (hereinafter referred to as a film forming step).

 [0072] (Installation of container on film forming apparatus)

First, a vent (not shown) is opened to open the vacuum chamber 6 to the atmosphere. In the reaction chamber 12, with the upper chamber 15 removed, the plastic container 11 is inserted and accommodated from the upper opening of the lower chamber 13. 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. And the top When the chamber 15 contacts the lower chamber 13 via the O-ring 14, the reaction chamber 12 is closed. 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. Lean! /

 [0073] 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 beverages such as beer, sparkling liquor, carbonated beverages, fruit juice beverages, and soft drinks. Moreover, either a returnable container or a one-way container may be used.

 [0074] The resin used in 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 (CO C, cyclic olefin copolymer), ionomer resin, poly-4-methylpentene 1 resin, polymethyl methacrylate resin, polystyrene resin, ethylene-butyl alcohol copolymer resin, acrylonitrile resin, polychlorinated bur resin, polychlorinated Examples include vinylidene resin, polyamide resin, polyamideimide resin, polyacetal resin, polycarbonate resin, polysulfone resin, or tetrafluoroethylene resin, acrylonitrile styrene resin, acrylonitrile-butadiene-styrene resin. Can do. Of these, PET is particularly preferred.

 [0075] (Decompression step)

Next, after closing the vent (not shown), the exhaust pump (not shown) is operated to open the vacuum valve 8, whereby the air in the reaction chamber 12 is exhausted. At this time, not only the inner 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 a required pressure, for example, 1 to 100 Pa, preferably 10 to OOPa is reached. This requires an exhaust time at a pressure of less than lPa, and the film formation speed may decrease, resulting in an increase in film formation cost. Also, higher pressure than lOOPa As a result, pyrolyzed and oxidized non-pyrophoric raw materials may become particles in the gas phase.

[0076] (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 a force depending on the type of non-pyrophoric raw material, for example, 300 to 1800 ° C. 800

~; 1100 ° C is more preferred. 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.

[0077] (Film formation process)

 Thereafter, the gas flow rate regulator 24a supplies a non-pyrophoric raw material at a predetermined flow rate, and the gas flow rate regulator 24b supplies a predetermined flow rate of ozone gas. The non-pyrophoric raw material and ozone gas are passed through the raw material gas supply pipe 23 and placed in the plastic container 11 that has been depressurized to a predetermined pressure. It blows out toward the wire 18. 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 beginning of film formation, the hot wire 18 decomposes ozone into radical oxygen, which oxidizes the pyrolyzed non-pyrophoric material. 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 a key element as a constituent element, a non-pyrophoric key organic compound is preferable. On the other hand, examples of pyrophoric materials include silane-based materials such as monosilane, disilane, and trisilane. By using a chelated organic compound such as trimethylsilane as a non-pyrophoric raw material and thermally decomposing with the hot wire 18, a SiO thin film can be formed as an oxide thin film.

[0079] As the non-pyrophoric key organic compound, for example, trimethylsilane, hexamethyldisiloxane, phenylsilane, or hexamethylsilazane is preferable. Dimethyoxy silane, tetramethoxy silane, tetra methino silane, dimethoxy methino silane, etokineto Limethylsilane, diethoxymethylsilane, ethoxydimethylvinylsilane, allyltrimethylenosilane, methoxydimethylenosilane, trinoethylenosilane, hexamethinoresinsilane, methoxymethylvinylsilane, triethoxymethylsilane, triethoxybutylsilane, bis (t Limethylsilyl) acetylene, tetraethoxysilane, trimethoxyphenylsilane, _Ί —Dari

Propyl (trimethoxy) silane, dihydroxydiphenylsilane, diphenylsilane, triethoxyphenylsilane, tetraisopropoxysilane, dimethoxydiphenylsilane, methoxydiphenylsilane, tetra-η-butoxysilane, tetraphenoxysilane or poly (meth) Lehydrogensiloxane).

 [0080] As the non-pyrophoric raw material, in addition to the non-pyrophoric key organic compound, a raw material containing a metal element as a constituent element, for example, a non-pyrophoric metal such as an organometallic compound or a metal alkoxide It may be an element-containing organic compound. If the metal element is, for example, an alcoholium, an alkoxide raw material that is preferably a non-pyrophoric aluminum-containing organic compound is more preferable. For example, tritertiary butoxy aluminum (Al (t-OC H)), triethoxy aluminum (Al (OC H)), triisopropoxy

 4 9 3 2 5 3

 Luminium (Al (i-OC H)), trisecondary butoxy aluminum (Al (sec- OC H))

 3 7 3 4 9

), Trisacetylacetonate aluminum (A1 (C H O)) or tris dipivaloilme

3 5 7 2 3

 There is tannate aluminum (A1 (C H O)). On the other hand, as a pyrophoric raw material,

 11 19 2 3

 There is chill aluminum. For example, triisopropoxy aluminum is used as a non-pyrophoric raw material and is thermally decomposed with hot wire 18 to measure the power of forming an AIO thin film as an oxide thin film.

[0081] In this embodiment, the reason why the non-pyrophoric raw material and ozone are supplied 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 must be formed at a low temperature as long as the plastic material is used, a highly efficient precipitation reaction can be performed at a low temperature even at a low temperature. Must be realized on the surface. Secondly, when an oxide thin film is produced by pyrolyzing and oxidizing non-pyrophoric raw materials with high safety! / Even if oxygen is supplied together, acid The force that did not cause the precipitation of the chemicals. Therefore, by supplying ozone with extremely strong oxidizing power together with non-pyrophoric raw materials, it is possible to thermally decompose and oxidize non-pyrophoric raw materials to efficiently produce oxide thin films. It has been found that it is possible to form a film on a plastic container having a shape. It is thought that ozone decomposes as shown in chemical formula 1 when heated to ultraviolet rays or above 200 ° C.

 (Chemical 1) 0 → O + ο

 3 2

 Therefore, when ozone is heated with the hot wire 18, it decomposes according to chemical formula 1, and radical oxygen exhibits strong oxidizing power. At the same time, the non-pyrophoric raw material is heated with the hot wire 18! /, So the non-pyrophoric raw material is thermally decomposed by the heat of the wire, or is decomposed by the catalytic action of the wire, and also by radical oxygen. Oxidized. As a result, an oxide thin film derived from a non-pyrophoric raw material is formed. Here, the hot wire 18 has at least two actions: (1) converting ozone into radical oxygen according to chemical formula 1, and (2) heating a non-pyrophoric raw material to thermally decompose or decompose by catalysis. do. The hot wire 18 is not necessarily required to have a catalytic action in the catalytic chemical vapor deposition method. The hot wire 18 only needs to be able to heat the non-pyrophoric raw material and ozone simultaneously. Of course, a form in which the hot wire 18 having catalytic action is used to promote thermal decomposition of the non-pyrophoric raw material by the catalytic action is not excluded from the present invention.

[0082] As described above, ozone is supplied by a commercially available ozonizer or ozone cylinder.

[0083] A non-pyrophoric raw material and ozone may be mixed with a dilution gas! /. As the diluting gas, for example, an inert gas such as argon or helium or a gas inert to a chemical reaction during film formation is used. Can be used to adjust the concentration of non-pyrophoric raw materials and the pressure in the vacuum chamber

[0084] The supply amount of ozone gas should be such that the carbon remaining in the oxide thin film is substantially zero. For example, the flow rate is 5 to 20 times that of non-pyrophoric substances. is there. 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. The gas barrier property is best when the carbon remaining in the oxide thin film is substantially zero.

[0085] Here, the supply amount of ozone gas is as follows. The amount of carbon remaining in the oxide thin film (for example, a flow rate of 0.5 to 2.0 times that of non-pyrophoric substances) It may be set to an amount that substantially becomes the mouth (for example, 5 to 20 times the flow rate for 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. Therefore, by making the gradient composition film so that carbon remains in the oxide thin film on the substrate surface and carbon does not remain on the surface side of the oxide thin film, the adhesion to the substrate is good. And it can be set as an oxide thin film with favorable gas-barrier property.

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

 [0087] When the wire 18 is a hot wire, the wire 18 is preferably formed using a metal or carbon that does not substantially volatilize as a main component. 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.

[0088] On the other hand, a volatile component derived from the wire may be incorporated into the oxide thin film as an additive component other than impurities. In order to carry out such a manufacturing method, the following steps are taken. The wire 18 is formed of a metal, a conductive metal compound, or carbon as a main component. When the wire 18 is used as a hot wire, the wire 18 volatilizes carbon, silicon, or metal element, and the carbon, silicon, or metal element is oxidized. It may be incorporated into a thin film 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 include molybdenum, copper, aluminum, and palladium. These metal elements volatilize when they are used as hot wires, and are incorporated into the oxide thin film. Become an ingredient. Specific examples of the conductive metal compound include, for example, FeC or FeCrC. When it is used as a hot wire, the carbon volatilizes and is incorporated into the oxide thin film to become an additive component. As a specific example of the form in which the wire 18 is formed of a metal as a main component and volatilizes the key when used as a hot wire, the wire 18 is formed on the surface of a wire of a non-volatile metal such as Ir, Pt, or NiCr. There are wires sputtered and coated with Si. When hot wire is used, the silicon volatilizes and is incorporated 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 into the oxide thin film as an additive component, the physical properties of the oxide thin film are improved. For example, when silicon is incorporated as an additive component in an oxide thin film, for example, an AIO thin film, flexibility is improved while maintaining gas noriality. The volatilized metal element is preferably taken into an oxide thin film such as a SiO thin film or an AIO 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, force donium, sulfur, selenium, gold, nickel, uranium, vanadium, silver, molybdenum, tin, and tan Gusten, bismuth or enolebium.

 [0089] In the present embodiment, the additive component preferably functions as a cross-linking material in the oxide thin film. It is possible to improve the physicochemical stability of the oxide thin film or adjust the refractive index. Specific examples of the additive component that functions as a cross-linking material are, for example, sodium, potassium, lithium, lead, carbon, or titanium. For example, if the oxide thin film is a SiO thin film, it can enter the network structure of SiO as a network decoration oxide or intermediate oxide by adding sodium, potassium or lithium, and the physicochemical properties such as thermal expansion coefficient and hardness You can adjust the properties. Similarly, the addition of lead can increase the refractive index. Similarly, when titanium is added, alkali resistance is improved. Similarly, adding carbon can add flexibility.

[0090] As another mode in which the oxide thin film is incorporated as an additive component, for example, the following is performed. In other words, 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. It is a form. 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 include molybdenum, copper, aluminum, palladium, tungsten, silver, silicon, or a compound containing these. The oxide thin film can be colored. In addition, by incorporating Cay as an additive into the AIO thin film, flexibility is improved while maintaining gas barrier properties. This form includes a form in which the constituent components of the wire 18 are not volatilized and a form in which the component is volatilized. In the latter case, both volatile materials and wire volatiles are incorporated into the oxide film as additive components.

Furthermore, in this embodiment, an oxide thin film may be formed in which a component derived from a non-pyrophoric raw material is a main component, and a component derived from a layer is also a main component. In other words, as such a form, the wire 18 is mainly composed 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. Vapor that is formed and contains at least one component of carbon, silicon, or metal volatilized from the hot wire is a non-pyrophoric caged organic compound or a non-pyrophoric aluminum-containing organic compound. In addition to the non-pyrophoric raw material, such as the above, it becomes a non-pyrophoric raw material, and the vapor oxidizes to form one of the main components of the oxide thin film. Specific examples of the metal include molybdenum, copper, aluminum, and palladium. These metal elements volatilize when used as a hot wire, and steam containing these metal elements becomes non-pyrophoric raw materials that are oxidized and contain non-pyrophoric key organic compounds or non-pyrophoric aluminum. Along with non-pyrophoric materials such as organic compounds, it is one of the main components of oxide thin films. Wire 18 1S A specific example of a mode in which the key is volatilized when it is formed as a main component and used as a hot wire, Si is applied to the surface of a wire of a non-volatile metal such as Ir, Pt or NiCr. Some wires are sputtered and coated. When hot wire is used, the volatilization of the vapor causes the vapor to become a non-pyrophoric raw material that is oxidized and non-pyrophoric key organic compounds or non-pyrophoric aluminum-containing organic compounds. Together with pyrophoric materials, it is one of the main components of oxide thin films. Conductive metal compounds are not used alone, but together with the two non-pyrophoric raw materials (steam containing metal element and steam containing key element) Used together. Specific examples of the conductive metal compound include, for example, FeC or FeCrC. Carbon is volatilized and oxidized when it is used as a hot wire, and is taken into the oxide thin film as an additional component.

[0092] The supply method of the non-pyrophoric raw material described above included a form in which the non-pyrophoric raw material is supplied via the raw material gas supply pipe 23. Another mode 1 in which only ozone gas is allowed to flow through the raw material gas supply pipe 23 without being supplied through the supply pipe 23 will be described. That is, the wire 18 is a wire formed of a metal, a conductive metal compound, or carbon containing at least one of carbon, carbon, or metal that volatilizes when used as a hot wire as a main component. To do. Then, when it becomes a hot wire, a vapor containing at least one component of carbon, silicon, or metal volatilized from the hot wire becomes a non-pyrophoric raw material. Specific examples of the metal include molybdenum, copper, aluminum, and palladium. When a hot wire is formed, these metal elements are volatilized, and the vapor containing these metal elements becomes a non-pyrophoric raw material, which is oxidized and becomes the main component of the oxide thin film of the metal element. As a specific example of the form in which the wire 18 is formed of a metal as a main component and volatilizes the key when used as a hot wire, Si is applied to the surface of a non-volatile metal wire such as Ir, Pt or NiCr. Some wires are sputtered and coated. When the hot wire is formed, the key volatilizes and this vapor becomes a non-pyrophoric raw material that is oxidized and becomes the main component of the SiO thin film. Conductive metal compounds are not used alone, but are used in combination with the two non-pyrophoric raw materials (steam containing metal elements and steam containing key elements). Specific examples of the conductive metal compound include, for example, FeC or FeCrC. Carbon is volatilized and oxidized when it is used as a hot wire, and is taken into the oxide thin film as an additive component. If the steam is derived from wire, the safety is further improved and the means for introducing the raw material is simplified. Moreover, the composition of the thin film can be easily controlled by adjusting the composition of the wire. In addition, the raw material introduction means is simplified. Steam from the wire is preferably a vapor of a compound containing elemental or the metal of the metal saturated vapor pressure of more than 10_ ⁴ Pa below 2000 ° C. A sufficient film formation rate, for example, a film formation rate of 2.5 nm / second or more can be obtained.

[0093] Examples of the vapor include molybdenum, copper, aluminum, palladium, and tungsten. Vapor containing silver or silicon (1). 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. Also vapor containing carbon, sodium, potassium, lithium, lead or titanium

(2) may be present simultaneously with the steam (1). The vapor (1) is oxidized to form an oxide thin film, and the elements contained in the vapor (2) are taken into the oxide thin film as an additive component.

 [0094] In another embodiment 1 in which only the ozone gas is allowed to flow through the source gas supply pipe 23 without being supplied through the source gas supply pipe 23, a volatile substance is applied or supported on the surface of the wire to form a hot wire. Volatile substances may be volatilized and incorporated into the oxide thin film as an additive component. It is possible to form 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 added component. Alternatively, a volatile substance is applied or supported on the surface of the wire to volatilize the volatile substance when used as a hot wire, and the volatile substance is oxidized as a non-pyrophoric raw material together with the vapor volatilized from the wire. You may make it become a main component of a physical thin film. It is possible to form an oxide thin film in which the component derived from the wire is the main component and the component derived from the volatile substance carried on the wire is also the main component. If the main component derived from the non-pyrophoric raw material and the main component derived from the wire are the same, the oxide constituting the oxide thin film becomes a single component oxide thin film such as a SiO thin film or an AIO thin film. If the main component derived from non-pyrophoric raw material is different from the main component derived from wire, a double oxide oxide thin film is formed. An example of the double oxide is Si Mo 2 O. The volatile substance is a substance that becomes an oxide when oxidized, and is, for example, molybdenum, copper, aluminum, noradium, silicon, or a compound containing these, and these are preferably powders.

[0095] Further, 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. Volatile substances coated or supported on the surface of wire 18 are used as non-pyrophoric materials. 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 is used. These are preferably powders. An oxide thin film of these elements is obtained. The oxide thin film derived from volatile substances can be obtained safely by the oxidation action of ozone. In addition, 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.

 [0096] When sodium, potassium, or lithium is volatilized as a volatile substance, it is unstable by itself, so these salts such as carbonates and oxalates are supported on wires.

 [0097] (Finished 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 wire 18, the pressure in the plastic container 11, the supply gas flow rate, the time that the non-pyrophoric raw material and ozone gas 33 are blown onto the wire 18, the type of non-pyrophoric raw material, etc. 5 ~;! OOnm is preferable. According to the above embodiment, the film formation rate is as high as 2.5 to 4. Onm / 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 to an uncoated plastic container. .

 [0098] When an oxide thin film is formed on the outer surface of the plastic container 11, the film is formed in a state where the plastic container 11 is rotated by the bottle rotating mechanism 32 in order to improve the uniformity of the film. I'd prefer to do it.

[0099] Next, an embodiment in which mass production is performed in the method for manufacturing a plastic container coated with an oxide thin film according to the present 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 placed in the vacuum chamber 6 that is set to a predetermined pressure (for example, 10 to; In order to achieve this state, a process of adding the plastic container 11 into the vacuum chamber 6 through the 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 hot In order to efficiently bring the non-pyrophoric raw material heated by the wire and ozone into contact with the surface of the plastic container 11, the plastic container 11 is attached to the wire 18 installed in the transfer path in the vacuum chamber. A process of transporting along the transport path is added so that the surface of the plastic container 11 approaches a desired distance (for example, 5 to 5 Omm). 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 the differential pressure mechanism is further added. By adding the above steps, it is possible to efficiently mass-produce plastic containers coated with an oxide thin film.

 Example

[0100] (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 was about 0.3 mm. Iridium wire was used as 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 of the bottle was about 30 mm. A direct current was applied to the iridium wire to form a 800 ° C hot wire. The pressure in the vacuum chamber 6 during film formation was 20 Pa. The film formation time was 15 seconds. The PET bottle coated with the obtained silicon oxide thin film was designated as Example 1. Example 1 was evaluated as follows.

[0101] (Evaluation method)

 (1) Oxygen permeability

 The oxygen permeability of this container was measured under the conditions of 23 ° C. and 90% RH using Oxtran 2/20 manufactured by Modern Control, and the measured value after 72 hours from the start of nitrogen gas replacement was described.

 (2) Film thickness

 The film thickness of DLC was measured using Veeco DEKTAK3.

 (3) Adhesion

Immerse the oxide thin film sample formed on the inner surface of the PET bottle purely at 25 ° C for one week. Pickled. About the comparatively smooth fixed part of PET bottles, the location which can measure film thickness was provided using masking, and the film thickness before and behind immersion was measured by the above-mentioned method. The samples with the same film thickness before and after immersion were judged to have adhesion, and the samples with significantly reduced film thickness before and after immersion were judged to have no adhesion.

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

[table 1]

[0103] (Example 2)

 Ozone was diluted to 3% with oxygen to make a mixed gas, this mixed gas was supplied at lOOsccm, and a film was formed in the same manner as in Example 1 except that the chemical film time was 50 seconds. Table 1 shows the deposition conditions and results.

[Example 3]

 Except that the pressure at the time of film formation was lOPa, film formation was performed in the same manner as in Example 1 to obtain Example 3. Table 1 shows the deposition conditions and results.

[0105] (Example 4)

 Except that the pressure at the time of film formation was lOOPa, film formation was performed in the same manner as in Example 1 to obtain Example 4. Table 1 shows the deposition conditions and results.

[0106] (Example 5)

 Ozone is diluted to 3% with oxygen to make a mixed gas, and this mixed gas is supplied at lOOsccm for 7.5 seconds to form a film, and then ozone is diluted to 10% with oxygen to make a mixed gas. Film formation was carried out in the same manner as in Example 1 except that the mixed gas was supplied for 7.5 seconds at lOOsccm, and the oxide thin film was changed to a gradient composition film having a different carbon concentration. . Table 1 shows the deposition conditions and results. The 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]

 Example 6 was carried out in the same manner as in Example 1 except that hexamethyldisiloxane was used as a non-pyrophoric material. Table 1 shows the deposition conditions and results.

[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. Table 1 shows the deposition conditions and results.

[Example 8]

 A film was formed in the same manner as in Example 1 except that hexamethyldisilazane was used as a non-pyrophoric raw material, and Example 8 was obtained. Table 1 shows the deposition conditions and results.

[0110] (Example 9)

Triisopropoxy aluminum is used as a non-pyrophoric raw material, and aluminum oxide A film was formed in the same manner as in Example 1 except that a thin film was formed. Table 1 shows the deposition conditions and results.

 [0111] (Example 10)

 Using the film forming apparatus 100 shown in FIG. 2, a film was formed on the inner surface of the PET bottle as in Example 1. Molybdenum wire was used as wire 18, and non-pyrophoric raw material was molybdenum vapor generated from molybdenum wire. Ozone was diluted to 10% with oxygen to make a mixed gas, and this mixed gas was supplied to lOOsccm. 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 of the bottle was about 30 mm. A direct current was applied to the molybdenum wire to make a 800 ° C hot wire. The pressure in the vacuum chamber 6 during film formation was 5 Pa. The film formation time was 30 seconds. The PET bottle coated with the obtained molybdenum oxide thin film was designated as Example 10. Example 10 was evaluated in the same manner as Example 1. Table 1 shows the deposition conditions and results. The obtained molybdenum oxide thin film was colored blue.

 [0112] (Example 11)

 Using the film forming apparatus 100 shown in FIG. 2, a film was formed on the inner surface of the PET bottle as in Example 1. Iridium wire was used as wire 18, and the non-pyrophoric material was aluminum powder, which is a volatile substance supported on the surface of iridium wire. The ozone was diluted to 10% with oxygen to make a mixed gas, and this mixed gas was supplied by lOOsccm. 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 of the bottle was about 30 mm. A direct current was applied to the iridium wire to obtain a 800 ° C hot wire. 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. Example 11 was evaluated in the same manner as in Example 1. Table 1 shows the deposition conditions and results.

 [0113] (Example 12)

Using the film forming apparatus 100 shown in FIG. 2, a film was formed on the inner surface of the PET bottle as in Example 1. Trimethylsilane as a non-pyrophoric material was supplied 1.5s _CC m. Molybdenum wire was used as the wire 18, and molybdenum wire generated from the molybdenum wire was incorporated into the silicon oxide thin film as an additive component. 20% ozone with nitrogen The mixed gas was diluted to 20 sccm and supplied. The distance between the wire 18 and the bottom surface inside the bottle was set to 30 mm. The distance between the wire 18 and the inner side of the bottle was about 3 Omm. A direct current was applied to the molybdenum wire to make a 800 ° C hot wire. The pressure in the vacuum chamber 6 during film formation was lOPa. The film formation time was 15 seconds. A PET bottle coated with a thin film of silicon oxide in which molybdenum was incorporated as an additive was obtained as Example 12. For Example 12, the same evaluation as in Example 1 was performed. Table 1 shows the deposition conditions and results. The silicon oxide thin film in which molybdenum was incorporated as an additive component was colored blue.

[0114] (Comparative Example 1)

 Film formation was performed on the outer surface of a round 500 ml PET bottle as a plastic container 11 using the film formation apparatus 200 shown in FIG. The wall thickness of the container was about 0.3 mm. Iridium wire was used as 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 of the bottle was about 55 mm. A direct current was applied to the iridium wire to form a 800 ° C hot wire. The pressure in the vacuum chamber 6 during film formation was 20 Pa. The film formation time was 15 seconds. The PET bottle coated with the obtained silicon oxide thin film was designated as Comparative Example 1. Table 1 shows the deposition conditions and results. 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. For this reason, gas barrier properties with a small film forming speed and a small film thickness were not obtained.

 [0115] (Example 13)

 Perform film formation 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 is 3 mm, and the distance between the wire 18 and the outer side surface of the bottle is about 3 mm. Example 13 was used. Table 1 shows the deposition conditions and results. As the distance between the force wire 18 obtained and the bottle surface was as short as 3 mm, the film formation in the vicinity of the gas blowing hole 17x was excessive, resulting in unevenness.

[0116] (Comparative Example 2) A film was formed in the same manner as in Example 1 except that the pressure during film formation was changed to lOPa, and Comparative Example 2 was obtained. Table 1 shows the deposition conditions and results. When trimethylsilane was used as a 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. A powder was formed. As a result, particles were deposited on the surface of the bottle, which was not formed by film formation. The adhesion was “none”.

[0117] (Example 14)

 Except that the pressure at the time of film formation was 8 Pa, film formation was carried out in the same manner as in Example 1 to obtain Example 14. Table 1 shows the deposition conditions and results. When trimethylsilane was used as a non-pyrophoric raw material, the pressure during film formation was too low, and although the gas barrier property was obtained, the film formation rate decreased.

[0118] (Comparative Example 3)

 A film was formed in the same manner as in Example 1 except that lOOsccm was supplied in place of ozone, and Comparative Example 3 was obtained. Table 1 shows the deposition conditions and results. No silicon oxide thin film was 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. Table 1 shows the deposition conditions and results. The force at which a silicon oxide thin film equivalent to that in Example 1 was formed and the deterioration of the tungsten wire were observed.

 [0120] (Example 16)

Using the film forming apparatus 100 shown in FIG. 2, a film was formed on the inner surface of the PET bottle as in Example 1. Tungsten wire was used as wire 18, and the non-pyrophoric material was tungsten vapor generated from the tungsten wire. Ozone was diluted to 10% with oxygen to make a mixed gas, and this mixed gas was supplied by lOOsccm. 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 of the bottle was about 30 mm. A direct current was applied to the tungsten wire to make a 2000 ° C hot wire. The pressure in the vacuum chamber 6 during film formation was 5 Pa. The film formation time was 30 seconds. The PET bottle coated with the obtained tungsten oxide thin film was designated as Example 16. About Example 16 The same evaluation as in Example 1 was performed. Table 1 shows the deposition conditions and results. 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, a film was formed on the inner surface of the PET bottle as in Example 1. Trimethylsilane as a non-pyrophoric material was supplied 1.5s _CC m. In addition, a tungsten wire was used as the wire 18, and tungsten vapor that also generates tungsten wire force was incorporated as an additive into the silicon oxide thin film. 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 inside the bottle was 30 mm. The distance between the wire 18 and the inner side of the bottle was about 30 mm. A direct current was applied to the tungsten wire to make a hot wire of 2000 ° C. The pressure in the vacuum chamber 6 during film formation was l OPa. The film formation time was 15 seconds. A PET bottle coated with a thin film of silicon oxide in which tungsten was incorporated as an additive component was obtained as Example 17. Example 17 was evaluated in the same manner as in Example 1. Table 1 shows the deposition conditions and results. The silicon oxide thin film in which tungsten was incorporated as an additive component was colored dark.

 [0122] (Comparative Example 4)

[0123] With respect to Example 1, composition analysis of depth-wise silicon, carbon, and oxygen was performed by X-ray photoelectron spectroscopy (XPS). The results are shown in FIG. Similarly, Example 2 is shown in FIG. In FIG. 12, there was no residual carbon in the silicon oxide thin film (below the detection limit), but in FIG. 13, 8 atom% residual carbon remained in the silicon oxide thin film. Therefore, ozone was found to contribute to reducing residual carbon in the silicon oxide thin film.

 Industrial applicability

[0124] 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.

Claims

The scope of the claims  [1] A step of setting the inside of the vacuum chamber containing the plastic container to a predetermined pressure below atmospheric pressure;  Energizing a wire disposed inside the vacuum chamber to generate a hot wire by generating heat above a predetermined temperature;  The non-pyrophoric raw material containing ozone or a metal element as a constituent element and ozone gas supplied to the inside of the vacuum chamber are heated by the hot wire, and then at least the inner surface or the outer surface of the plastic container Contacting any one of them, and forming 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:  [2] The plastic container is carried into the vacuum chamber via a differential pressure mechanism;  The plastic container is transported on the transport path so that the surface of the plastic container approaches a desired distance from 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 unloading the plastic container to the outside of the vacuum chamber via a differential pressure mechanism.  [3] The method for producing a plastic container coated with an oxide thin film according to [1] or [2], wherein in the step of forming the oxide thin film, the plastic container is irradiated with ultraviolet rays.  [4] A non-pyrophoric key organic compound is used as the non-pyrophoric raw material and decomposed by a thermal decomposition reaction or catalytic reaction with the hot wire to form a SiO thin film as the oxide thin film. Alternatively, a non-pyrophoric ano-reductive 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 AIO 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. [5] The supply amount of the ozone gas is such that carbon remaining in the oxide thin film is substantially zero. The method for producing a plastic container coated with an oxide thin film according to claim 4, wherein  [6] The supply amount of the ozone gas is set so that 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 to increase the carbon remaining in the oxide thin film. 5. The oxide thin film according to claim 4, wherein the oxide thin film is a gradient composition thin film having a carbon content that varies in the thickness direction. Manufacturing method of coated plastic container.  [7] The wire according to claim 1, 2, 3, 4, 5 or 6, characterized in that, when the hot wire is used as a hot wire, the wire is formed mainly of a metal or carbon that does not substantially volatilize. The manufacturing method of the plastic container which coat | covered the oxide thin film of description.  [8] The wire is formed of a metal, a conductive metal compound, or carbon as a main component, and when the hot wire is used, volatilizes carbon, silicon, or a metal element, and the carbon, 7. The method for producing a plastic container coated with an oxide thin film according to claim 1, wherein a metal element is incorporated into the oxide thin film and becomes an additive component.  [9] The method for producing a plastic container coated with an oxide thin film according to [8], wherein the additive component functions as a color center.  [10] The metal elemental force that functions as the color center Cobalt, manganese, copper, iron, chromium, antimony, force donium, sulfur, selenium, gold, nickel, uranium, vanadium, silver, molybdenum, tin, tungsten, bismuth or 10. The method for producing a plastic container coated with an oxide thin film according to claim 9, wherein the plastic container is erbium.  11. 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 production of a plastic container coated with an oxide thin film according to claim 11, wherein the additive component that functions as the cross-linking material is sodium, potassium, lithium, lead, carbon, or titanium. Method. [13] The wire is mainly composed 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. Vapor power that is formed as a component and contains at least one component of carbon, silicon, or metal volatilized from the hot wire Non-pyrophoric key organic compound or non-pyrophoric aluminum 5. The non-pyrophoric raw material together with the non-pyrophoric raw material such as a contained organic compound, and the vapor is oxidized to form one of the main components of the oxide thin film. A method for producing a plastic container coated with the oxide thin film described above.  [14] 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 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, and the oxide thin film is an oxide thin film obtained by oxidizing the vapor. A method for producing a plastic container coated with the oxide thin film according to claim 1, 2 or 3.  [15] The vapor is molybdenum, copper, aluminum, palladium, tungsten, silver, silicon, carbon, sodium, potassium, lithium, lead, titanium, or a compound containing these, and the oxide thin film is molybdenum, 15. The method for producing a plastic container coated with an oxide thin film according to claim 14, wherein an oxide of copper, aluminum, palladium, tungsten, silver, or silicon is a main component.