WO2008062730A1 - Procédé de production de containers en plastique enrobés d'une fine pellicule d'oxyde - Google Patents

Procédé de production de containers en plastique enrobés d'une fine pellicule d'oxyde Download PDF

Info

Publication number
WO2008062730A1
WO2008062730A1 PCT/JP2007/072296 JP2007072296W WO2008062730A1 WO 2008062730 A1 WO2008062730 A1 WO 2008062730A1 JP 2007072296 W JP2007072296 W JP 2007072296W WO 2008062730 A1 WO2008062730 A1 WO 2008062730A1
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
oxide thin
wire
plastic container
raw material
Prior art date
Application number
PCT/JP2007/072296
Other languages
English (en)
Japanese (ja)
Inventor
Masaki Nakaya
Original Assignee
Kirin Beer Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kirin Beer Kabushiki Kaisha filed Critical Kirin Beer Kabushiki Kaisha
Publication of WO2008062730A1 publication Critical patent/WO2008062730A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45572—Cooled nozzles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45578—Elongated nozzles, tubes with holes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/46—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for heating the substrate

Definitions

  • 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.
  • the present invention relates to a method for manufacturing a plastic container. Background art
  • 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.
  • 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.
  • Patent Document 2 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).
  • a silicon oxide thin film is formed by plasma CVD as in Patent Document 1.
  • 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).
  • 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).
  • 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)
  • 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.
  • the cost of the device itself is less than the cost of the plasma CVD film forming device.
  • 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.
  • the present invention is mainly directed to plastic containers for beverages and foods.
  • 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.
  • raw materials containing halogens are generally avoided and are not practical from the viewpoint of the present invention.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present inventor has intensively developed to solve the above-mentioned problems.
  • 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.
  • 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.
  • 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.
  • the hot wire means a wire that is resistance-heated by energization.
  • the method for producing a plastic container coated with an oxide thin film 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.
  • 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.
  • 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.
  • an oxide thin film can be formed at high speed on the surface of a plastic container.
  • the plastic container coated with an oxide thin film 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.
  • UV irradiation promotes the decomposition of ozone to increase the oxidizing power and promotes the oxidation of non-pyrophoric raw materials.
  • the non-pyrophoric raw material and ozone gas are heated by the hot wire. The reaction can proceed.
  • 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.
  • an AIO thin film is formed as the oxide thin film by being decomposed by a catalytic reaction.
  • non-pyrophoric raw materials such as non-pyrophoric key organic compounds or non-pyrophoric aluminum-containing organic compounds such as silane-based materials or trimethylaluminum
  • pyrophoric raw materials such as non-pyrophoric key organic compounds or non-pyrophoric aluminum-containing organic compounds such as silane-based materials or trimethylaluminum
  • 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 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.
  • the gas nooricity becomes the best.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a component derived from a non-pyrophoric raw material as a main component
  • a component derived from a wire as an additive component, the types of functional thin films that can be formed can be easily diversified.
  • 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.
  • 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.
  • the additive component that functions as the cross-linking material is sodium, potassium, lithium, lead, carbon, or titanium. Is included.
  • 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.
  • the wire 1 contains at least one component of carbon, silicon, or metal that volatilizes when the hot wire is used.
  • 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.
  • 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.
  • the wire contains at least one component of carbon, silicon, or metal that volatilizes when the hot wire is used.
  • 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.
  • the steam is saturated steam pressure 10- 4 Pa or more below 2000 ° C
  • 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.
  • these additional vapors may be added.
  • a volatile substance is applied or supported on the surface of the wire, and the volatile substance is volatilized when the hot wire is formed.
  • the volatile substance volatilizes and the volatilization occurs.
  • the non-pyrophoric raw material can be selected as a main component of the oxide thin film.
  • 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.
  • the volatile substance is molybdenum, copper, aluminum, palladium, tungsten, silver, or a compound containing these.
  • Oxide thin films with different colors depending on the metal species can be obtained. The invention's effect
  • 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 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 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 ⁇ -- ⁇ '' is shown. .
  • FIG. 2 is a schematic conceptual diagram of a device for sulling and laying down. .
  • FIG. 2 is a schematic conceptual diagram of an apparatus for laying down. .
  • FIG. 2 is a schematic conceptual diagram of a device for depositing a film. .
  • FIG. 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. 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.
  • the vacuum chamber 6 includes a lower chamber 13 and an upper chamber 15 that is detachably attached to the upper portion of the lower chamber 13 and seals the inside of the lower chamber 13 with an O-ring 14. .
  • the upper chamber 15 has an upper and lower drive mechanism (not shown) and moves up and down as the plastic container 11 is carried in and out.
  • the internal space of the lower chamber 13 is formed to be slightly larger than the outer shape of the plastic container 11 accommodated therein.
  • the plastic container 11 is a beverage bottle, but may be a container used for other purposes.
  • the inside of the vacuum chamber 6, particularly the inside of the lower chamber 13, has an inner surface 28 that is a black inner wall or an inner surface that has a surface roughness 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).
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • the wire 18 is energized and generates heat to form a hot wire, the temperature of the source gas channel 17 rises.
  • 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.
  • the material of the source gas supply pipe 23 is preferably an insulator and has a high thermal conductivity.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the wire 18 is preferably made of a metal, particularly an oxidation-resistant metal.
  • a metal particularly an oxidation-resistant metal.
  • the wire 18 may be a carbon-based object such as carbon fiber.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the inner diameter of the mouth 21 is approximately 21 ⁇ 7 ⁇ 39.8 mm.
  • 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
  • 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.
  • 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.
  • 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.
  • 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!
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the wires 18a and 18b It is preferable that the portions are arranged to face different directions. In Fig.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 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
  • FIG. 4B shows a case where the wire has a coil spring shape.
  • 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.
  • 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! /
  • 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!
  • 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.
  • 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.
  • 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!
  • 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.
  • 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.
  • the wire 18 is a pair, the effect of improving the uniformity of film formation is high.
  • each is wound in parallel and a plurality of ring-shaped wires are arranged in parallel.
  • the uniformity of the film thickness can be improved.
  • the plastic container 11 may be formed by rotating the plastic container 11 around the main axis by the bottle rotating mechanism 32.
  • 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.
  • 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.
  • the wire 18 is disposed along the blowing direction of the non-pyrophoric raw material and ozone gas.
  • 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.
  • 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.
  • 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 77 ⁇ .
  • the gas blowing holes 77 ⁇ 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 77 ⁇ . 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.
  • 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.
  • the length of the source gas supply pipe 73 is preferably formed such that the distance L3 from the gas blowing hole 77 ⁇ 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.
  • a wire may be arranged in the source gas supply pipe as in the case of FIG.
  • 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.
  • 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.
  • 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.
  • 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! /
  • 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.
  • 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!
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • wires 18 are arranged along the side walls of the chamber.
  • the desired distance between the wire 18 and the surface of the plastic container for example, 5 to 50 mm is approached.
  • 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.
  • 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.
  • FIG. 10A shows a case where a film is formed on the inner surface of the plastic container
  • FIG. 10B shows a case where a film is formed on the outer surface of the plastic container. As shown in FIG.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a gas such as cooling nitrogen gas or cooling carbon dioxide gas
  • FIG. 11 shows another embodiment of the thin film forming chamber 42 shown in FIG.
  • 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.
  • 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.
  • the method for producing a plastic container coated with an oxide thin film 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
  • 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).
  • a vent (not shown) is opened to open the vacuum chamber 6 to the atmosphere.
  • the plastic container 11 is inserted and accommodated from the upper opening of the lower chamber 13.
  • 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.
  • 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! /
  • 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.
  • a returnable container or a one-way container may be used.
  • 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.
  • PET polyethylene terephthalate resin
  • PP polypropylene resin
  • cycloolefin copolymer 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.
  • the exhaust pump (not shown) is operated to open the vacuum valve 8, whereby the air in the reaction chamber 12 is exhausted.
  • 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.
  • higher pressure than lOOPa As a result, pyrolyzed and oxidized non-pyrophoric raw materials may become particles in the gas phase.
  • 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
  • the hot wire 18 is arrange
  • the gas flow rate regulator 24a supplies a non-pyrophoric raw material at a predetermined flow rate
  • 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.
  • 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.
  • a non-pyrophoric key organic compound is preferable.
  • examples of pyrophoric materials include silane-based materials such as monosilane, disilane, and trisilane.
  • non-pyrophoric key organic compound for example, trimethylsilane, hexamethyldisiloxane, phenylsilane, or hexamethylsilazane is preferable.
  • 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
  • Luminium Al (i-OC H)
  • trisecondary butoxy aluminum Al (sec- OC H)
  • 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.
  • 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.
  • 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.
  • 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.
  • ozone is supplied by a commercially available ozonizer or ozone cylinder.
  • a non-pyrophoric raw material and ozone may be mixed with a dilution gas! /.
  • a 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
  • the supply amount of ozone gas should be such that the carbon remaining in the oxide thin film is substantially zero.
  • 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.
  • 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).
  • 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.
  • 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.
  • the plastic container 11 it is preferable to irradiate the plastic container 11 with ultraviolet rays during film formation.
  • V ⁇ ultraviolet irradiation means is not shown.
  • the surface of the plastic container 11 can be sterilized.
  • 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.
  • 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.
  • 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.
  • the metal is preferably an oxidation resistant metal.
  • Ir, Re, Ni, Pt or Au an oxide thin film derived from a non-pyrophoric raw material with few impurities can be formed.
  • a volatile component derived from the wire may be incorporated into the oxide thin film as an additive component other than impurities.
  • the wire 18 is formed of a metal, a conductive metal compound, or carbon as a main component.
  • 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.
  • 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.
  • the conductive metal compound include, for example, FeC or FeCrC.
  • the carbon volatilizes and is incorporated into the oxide thin film to become an additive component.
  • 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.
  • the silicon volatilizes and is incorporated into the oxide thin film to become an additive component.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the addition of lead can increase the refractive index.
  • titanium alkali resistance is improved.
  • adding carbon can add flexibility.
  • the oxide thin film is incorporated as an additive component, for example, the following is performed.
  • 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.
  • the volatile substance include molybdenum, copper, aluminum, palladium, tungsten, silver, silicon, or a compound containing these.
  • the oxide thin film can be colored.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a non-volatile metal such as Ir, Pt or NiCr.
  • 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.
  • 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.
  • 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.
  • the metal include molybdenum, copper, aluminum, and palladium.
  • these metal elements 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.
  • Si is applied to the surface of a non-volatile metal wire such as Ir, Pt or NiCr. Some wires are sputtered and coated.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • Non-pyrophoric raw material 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.
  • the raw material introduction means is simplified.
  • an oxide thin film exhibiting color can be obtained.
  • the thin film 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.
  • the film formation rate is as high as 2.5 to 4. Onm / second, for example.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • the film thickness of DLC was measured using Veeco DEKTAK3.
  • 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.
  • 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 shows the deposition conditions and results.
  • Example 4 shows the deposition conditions and results.
  • 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 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.
  • 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.
  • 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
  • Example 11 was evaluated in the same manner 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.
  • 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.
  • Example 12 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.
  • 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.
  • 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.
  • 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.
  • 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”.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 tungs
  • 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.
  • 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.
  • 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.
  • 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.
  • XPS X-ray photoelectron spectroscopy
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Chemical Vapour Deposition (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)

Abstract

L'invention concerne un procédé de production peu onéreux de containers en plastique enrobés d'une fine pellicule à barrière gazeuse dans lequel une fine pellicule avec une propriété de barrière gazeuse peut être formée en toute sécurité à vitesse élevée à partir de matières premières bon marché et dans lequel on peut utiliser un appareil de production ne requérant aucun équipement dispendieux. Ce procédé comprend les étapes suivantes : régler l'intérieur d'une chambre à vide (6) en y plaçant un container en plastique (11) à une pression donnée inférieure ou égale à la pression atmosphérique ; faire passer un courant électrique par un câble (18) disposé dans la chambre à vide afin d'obtenir de la sorte une chauffe à une température donnée ou supérieure à celle-ci afin que le câble soit converti en fil chaud ; chauffer à l'aide du fil chaud un gaz d'ozone et une matière première non pyrophorique contenant de la silicone ou un élément métallique en tant qu'élément constitutif, alimenté à l'intérieur de la chambre à vide, et effectuer ensuite un contact au moins soit avec la surface interne soit la surface externe du container en plastique afin de former ainsi une fine pellicule d'oxyde dérivée de la matière première non pyrophorique.
PCT/JP2007/072296 2006-11-20 2007-11-16 Procédé de production de containers en plastique enrobés d'une fine pellicule d'oxyde WO2008062730A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006313503A JP5063089B2 (ja) 2006-11-20 2006-11-20 酸化物薄膜を被膜したプラスチック容器の製造方法
JP2006-313503 2006-11-20

Publications (1)

Publication Number Publication Date
WO2008062730A1 true WO2008062730A1 (fr) 2008-05-29

Family

ID=39429663

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/072296 WO2008062730A1 (fr) 2006-11-20 2007-11-16 Procédé de production de containers en plastique enrobés d'une fine pellicule d'oxyde

Country Status (2)

Country Link
JP (1) JP5063089B2 (fr)
WO (1) WO2008062730A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8932676B2 (en) 2010-12-28 2015-01-13 Kirin Beer Kabushiki Kaisha Method for producing gas barrier plastic molded body
US9410245B2 (en) 2010-12-28 2016-08-09 Kirin Beer Kabushiki Kaisha Gas-barrier plastic molded product and manufacturing process therefor
TWI576242B (zh) * 2011-12-28 2017-04-01 Kirin Brewery Gas barrier plastic molded body and manufacturing method thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5566334B2 (ja) * 2010-12-28 2014-08-06 麒麟麦酒株式会社 ガスバリア性プラスチック成形体及びその製造方法
JP5706777B2 (ja) * 2011-07-25 2015-04-22 麒麟麦酒株式会社 ガスバリア性プラスチック成形体
JP5779044B2 (ja) * 2011-08-24 2015-09-16 麒麟麦酒株式会社 濡れ性の制御方法
WO2014103677A1 (fr) * 2012-12-26 2014-07-03 麒麟麦酒株式会社 Dispositif de dépôt de film mince
US9725802B2 (en) 2014-11-11 2017-08-08 Graham Packaging Company, L.P. Method for making pet containers with enhanced silicon dioxide barrier coating

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55152176A (en) * 1979-05-15 1980-11-27 Ulvac Corp Pipe internal coating equipment
JPS62216930A (ja) * 1986-03-17 1987-09-24 Seiko Epson Corp 色ガラスの製造方法
JPH05299013A (ja) * 1992-04-24 1993-11-12 Toshiba Corp 電子管の製造方法
JPH0693451A (ja) * 1992-09-11 1994-04-05 Toagosei Chem Ind Co Ltd シリコン酸化膜の製造方法
JPH06181200A (ja) * 1992-12-11 1994-06-28 Babcock Hitachi Kk 光励起ｃｖｄ方法
JP2005132781A (ja) * 2003-10-31 2005-05-26 Sanyo Chem Ind Ltd 誘引剤
JP2006264791A (ja) * 1998-07-01 2006-10-05 Toppan Printing Co Ltd プラスチック容器

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2910807B2 (ja) * 1991-10-25 1999-06-23 株式会社村田製作所 誘電体共振器装置、誘電体フィルタおよびそれらの製造方法
JP2006164791A (ja) * 2004-12-08 2006-06-22 Nec Tokin Corp 同軸コネクタ

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55152176A (en) * 1979-05-15 1980-11-27 Ulvac Corp Pipe internal coating equipment
JPS62216930A (ja) * 1986-03-17 1987-09-24 Seiko Epson Corp 色ガラスの製造方法
JPH05299013A (ja) * 1992-04-24 1993-11-12 Toshiba Corp 電子管の製造方法
JPH0693451A (ja) * 1992-09-11 1994-04-05 Toagosei Chem Ind Co Ltd シリコン酸化膜の製造方法
JPH06181200A (ja) * 1992-12-11 1994-06-28 Babcock Hitachi Kk 光励起ｃｖｄ方法
JP2006264791A (ja) * 1998-07-01 2006-10-05 Toppan Printing Co Ltd プラスチック容器
JP2005132781A (ja) * 2003-10-31 2005-05-26 Sanyo Chem Ind Ltd 誘引剤

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8932676B2 (en) 2010-12-28 2015-01-13 Kirin Beer Kabushiki Kaisha Method for producing gas barrier plastic molded body
US9410245B2 (en) 2010-12-28 2016-08-09 Kirin Beer Kabushiki Kaisha Gas-barrier plastic molded product and manufacturing process therefor
TWI576242B (zh) * 2011-12-28 2017-04-01 Kirin Brewery Gas barrier plastic molded body and manufacturing method thereof

Also Published As

Publication number Publication date
JP5063089B2 (ja) 2012-10-31
JP2008127053A (ja) 2008-06-05

Similar Documents

Publication Publication Date Title
WO2008062730A1 (fr) Procédé de production de containers en plastique enrobés d'une fine pellicule d'oxyde
KR101307040B1 (ko) 가스 배리어성 플라스틱 용기의 제조 장치, 그 용기의 제조 방법
EP1852522B1 (fr) Film depose par evaporation sous vide par un procede de depot chimique en phase vapeur assiste par plasma
TW578214B (en) Method of forming oxynitride film or the like and system for carrying out the same
CA2822599C (fr) Produit moule en matiere plastique a barriere contre les gaz et son procede de fabrication
JP5695673B2 (ja) ガスバリア性プラスチック成形体の製造方法
JP4954679B2 (ja) バリア膜被覆プラスチック容器の製造方法及びその製造装置
Choi et al. Characterization of al2o3 thin films fabricated at low temperature via atomic layer deposition on pen substrates
JP5566334B2 (ja) ガスバリア性プラスチック成形体及びその製造方法
TWI749620B (zh) 氧化膜形成裝置
AU2011236081B2 (en) Apparatus for manufacturing gas barrier plastic container, method for manufacturing the container, and the container
JP6786897B2 (ja) 高周波プラズマｃｖｄによる成膜法
JP2012122089A (ja) ガスバリア薄膜を備えるプラスチック成形体及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07832026

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07832026

Country of ref document: EP

Kind code of ref document: A1