MX2007014841A

MX2007014841A - Apparatus for manufacturing gas barrier plastic container, method for manufacturing the container, and the container.

Info

Publication number: MX2007014841A
Application number: MX2007014841A
Authority: MX
Inventors: Akio Mishima; Akira Shirakura; Masaki Nakaya
Original assignee: Kirin Brewery
Priority date: 2005-05-27
Filing date: 2006-05-26
Publication date: 2008-02-14

Abstract

This invention provides an apparatus for manufacturing a gas barrier plastic container that, in order to reduce the cost of the apparatus in the manufacture of a gas barrier plastic container, can simultaneously meet the requirements that an identical vacuum chamber can be used even in the case of a different container shape, the need to use a high-frequency power supply can be eliminated, and a film can be formed on a plurality of containers within one vacuum chamber. In an apparatus for forming a film on the inner surface of a container, a thermal catalyst is supported on a starting material gas feed pipe, and the starting material gas feed pipe is inserted into the port of the container, followed by film formation. In an apparatus for forming a film on the outer surface of a container, a thermal catalyst is disposed around the container, and a starting material gas is blown out through the starting material gas feed pipe while bringing the starting material gas into contact with the thermal catalyst for film formation. Cooling is carried out to avoid thermal deformation of the container by heat radiated from the thermal catalyst. For example, a container on which a hydrogen-containing SiN<sub>x</sub> thin film having a film thickness of 5 to 100 nm and having a hydrogen content of 1 to 10 atomic% has been formed, is obtained.

Description

"APPARATUS TO MANUFACTURE A PLASTIC CONTAINER OF GAS BARRIER, METHOD TO MANUFACTURE THE CONTAINER AND THE RECIPIENT" FIELD OF THE INVENTION The present invention relates to a beverage plastic container having oxygen gas and carbon dioxide gas barrier properties which is suitable for filling, for example, with content such as alcoholic beverages such as beer and the like. similar that oxidation is sensitive from the point of view of quality and requires that there be a limited release of carbon dioxide gas from the container wall, or soft drinks which are sensitive to oxidation in the same way, and in particular refers to a plastic container having a thin gas barrier film formed by a catalytic chemical vapor waste method in at least one of the outer surface and the inner surface as the oxygen gas and dioxide gas barrier layer carbon, which is cost-effective and light in weight, and which has superior shock resistance and recycling capacity, and a manufacturing method and its manufacturing apparatus.

BACKGROUND OF THE INVENTION Since ancient times, beer has been consumed habitually in Europe, and in recent years it has been consumed in large quantities as the alcoholic beverage of the masses throughout the world. In recent years, breweries brew large quantities of beer, and after filling small containers, it is transported to consumer areas, stored and sold. This kind of beer not only requires preserving the aroma during transport and storage, but because it is easily oxidized as it contains carbon dioxide it is used in low gas permeability containers such as glass bottles, aluminum cans and Similary. Aluminum cans are lightweight, have a higher recycling capacity, gas barrier properties, impact resistance and light blocking properties. According to the above, they are considered to be ideal containers as a container material for contents that oxidize easily as well as those that do not oxidize, and recently the use as beer containers has increased to occupy the current trend. On the other hand, the raw material is expensive, the manufacturing equipment such as the equipment for the aluminum cans and the filling equipment for the content need to be large scale and high performance, a capital investment is required and this can only be correspond to low mix mass production products. In addition, the aluminum material requires corrosion resistance treatment, the cost of the product is high, and it is difficult to manufacture large containers. In addition, viewing content is also an important concept for recipients in the food markets, but the content is not visible through them. For the reasons mentioned above, usually aluminum cans are used as small containers of one liter or less which are impossible to reseal. Glass bottles that are used massively have a higher recycling capacity, gas barrier properties, corrosion resistance and reseachability, may also correspond to a low volume, high mix production, and have the advantage that the Production can be carried out with a relatively low product cost. However, in comparison with plastic containers such as polyethylene terephthalate bottles (hereinafter referred to as "PET") and the like or aluminum cans, they have serious disadvantages such as the weight of the container being weighed and a resistance to them. very weak shocks. As a measure against this, the decision has been made to design the wall of the thin bottle in order to lighten the weight, but because there is a limit, the effect of it is trivial. According to the above, this market is in the process of gradually changing to aluminum cans and PET bottles.

BRIEF DESCRIPTION OF THE INVENTION In addition, the plastic containers are transparent and light in weight, have a greater resistance to shocks and greater resistance to corrosion, have a low product cost, only need a small investment for the equipment, and form a Superior packaging material able to correspond with a low volume and high mix production. However, the gas barrier properties are low, which is a problem that does not exist in aluminum cans and glass bottles. Particularly, plastic containers have serious disadvantages because the gas barrier properties for oxygen gas and carbon dioxide gas and the like are bad as containers of contents that are sensitive to oxidation from the point of view of quality and are sensitive to the discharge of carbon dioxide gas, for example, content such as beer and the like. Many measures have been proposed to improve the gas barrier properties of this class of plastic containers in which a resin layer of structural material and a resin layer of gas barrier property are laminated to realize a multi-layer plastic container. which have improved gas barrier properties. Regarding the prior art methods for manufacturing a multi-layer plastic container, there is a large number of proposals such as (1) a direct injection forming method (for example, see Patent Document 1) in which a parison is formed by extruding a thermoplastic plastic (structural resin) such as PET or polypropylene (hereinafter referred to as "PP") or the like and a gas barrier property resin such as a saponified material (alcohol copolymer of ethylene-vinyl, hereinafter referred to as "EVOH" - ethylene-vinyl alcohol copolymer) of ethylene-vinyl acetate copolymer, polyamide, polyvinylidene chloride, polyacrylonitrile or the like with such a gas barrier property resin that forms a intermediate layer, and then this experiences the formation of an air injection, (2) a method that applies a gas barrier resin such as EVOH or the like to the surface of a plastic container after it is formed (for example, see Patent Document 2), (3) and because the gas barrier properties decrease when the EVOH applied as described above absorbs moisture, in order to avoid this, a method wherein the surface of such a gas barrier property resin, particularly, the surface of the container is covered using a shrink film coated with a hydrophobic resin (e.g., see Patent Document 3), and the like. In addition, an injected multiple layer flexible plastic container capable of maintaining the high strength of the product even for thin walls anticipates the more developed method (for example, see Patent Document 4). However, even in this method, compared to the single layer plastic container of the prior art for soft drinks, the multi-layer plastic container has problems with productivity (forming cycle), the cost of the molding machine, costs such as the maintenance of the molding machine and the like, and have problems with the ability to recycle. From these fundamentals, there is a desire for a single layer PET bottle coated with a highly functional thin film that can be used by the general purpose PET bottle molding machine, and which satisfies the required performance as a beer container . In recent years, a DLC (Diamond Like Carbon) film has practical use as a thin layer film coated on PET bottles. This DLC film is a film formed from a three-dimensional amorphous structure by carbon atoms and hydrogen atoms, is hard, has superior insulating properties, has a high refractive index, and is a hard carbon film that has a very soft morphology. In the prior art, there are examples where this kind of DLC film-forming technology has been applied to plastic containers (for example, see Patent Document 5). The apparatus for forming a general DLC film described in Patent Document 5 as explained below. Particularly, as seen in Figure 9, a plastic container 5 is housed inside an outer electrode 2 placed inside a reaction chamber 1 having an introduction port IA and an output port IB of carbon source gas . Further, after a carbon source gas is introduced through the introduction port IA, a DLC is formed on the inner surface of the plastic container 5 by applying a high frequency energy with a high frequency energy supply 4 between an inner electrode 3 and the outer electrode 2 to excite the carbon source gas and to generate plasma.

BRIEF DESCRIPTION OF THE INVENTION However, the apparatus for forming a DLC film described above invariably requires the supply of high frequency energy 4 and a high frequency energy equivalency device (the number is not shown) given that the gas carbon source is decomposed by plasma and ionized, and then the ions accelerated by an electric field collide with the inner surface of the plastic container in order to form a thin film, and therefore, presents the problem of increases in cost of the device. Further, in the apparatus for forming a DLC film described above, the outer electrode 2 and the inner electrode 3, the reaction chamber 1 formed from the outer electrode 2 and the inner electrode 3 are required for a container are invariably required. plastic, and the outer electrode 2 must be made to correspond to each container shape, and this leads to an increasing cost of the DLC film forming apparatus. In addition, with the DLC film forming apparatus described above, when a thin film is formed, the plasma will damage the thin film surface, the good quality of the thin film will be easily ruined, and the hydrogen content ratio which causes the weakening of the gas barrier properties of the DLC film, and this makes it difficult to obtain 15 ~ 20 times greater gas barrier properties. In this regard, the present invention was developed to solve the problems of the prior art described above. Particularly, in an apparatus for manufacturing a gas barrier plastic container, an object of the present invention is to satisfy the condition that it is possible to use the same vacuum chamber even when the container shapes are different, provided that no a high frequency energy source is necessary, and the condition that the film formation can be realized for a plurality of containers inside a vacuum chamber in order to decrease the cost of the apparatus. On this point, an object of the invention is to provide a manufacturing apparatus that can form a thin gas barrier film on the inner surface of a plastic container, and a manufacturing apparatus that can form a thin gas barrier film on the outer surface of a plastic container. Furthermore, in a method of manufacturing a gas barrier plastic container, an object of the present invention is to form a thin gas barrier film which is not damaged by the plasma on at least some of the inner surface or the surface outside of a plastic container. Further, in a gas barrier plastic container, an object of the present invention is to impart both durability which makes it difficult to occur in cracks even when there is deformation or contraction of the container as gas barrier properties for oxygen gas and gas. carbon dioxide gas by forming a thin film of hydrogen-containing SiNx, a thin film of DLC containing hydrogen, a thin film of SiOx containing hydrogen or a thin film of SiCxNy with hydrogen content at a thickness of pre-established film and a preset hydrogen concentration that is not damaged by the plasma on at least some of the inner surface or outer surface of a plastic container. The present inventors discovered that it is possible to solve the problems described above by using a catalytic chemical vapor waste method when a thin gas barrier film is formed on the wall surface of a plastic container, and they completed the present invention. Particularly, the first apparatus for manufacturing a gas barrier plastic container according to the present invention comprises a vacuum chamber for housing a plastic container, a discharge pump evacuating the vacuum chamber, a source gas supply pipe formed from an insulating and heat resistant material which is configured to be inserted into and removable from the interior of the plastic container in order to supply a source into the plastic container, a thermal catalyst that is supported on the source gas supply pipe, and a heating energy supply from which it supplies electricity to the thermal catalyst to generate heat. The present manufacturing apparatus is an apparatus for manufacturing a gas barrier plastic container in which a thin gas barrier film is formed on the inner surface of the container. In the first apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the source gas supply line has a cooling line formed integrally to cool the source gas supply line. Because the temperature of the source gas supply pipe increases due to the heat generated by the thermal catalyst, upon cooling it, it is possible to reduce the thermal effects inflicted on the plastic container.

In the first apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the source gas supply pipe is a ceramic pipe formed from a material in which the aluminum nitride, silicon carbide, Silicon nitride an aluminum oxide forms main component. This makes it possible to supply electricity in a stable manner to the thermal catalyst, has durability, and makes it possible to discharge the heat efficiently by the thermal conduction of the heat generated by the thermal catalyst. In the first apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the source gas supply line has a gas ejection hole in the tip of the pipe, and the distance of the ejection orifice of the gas. gas at the bottom of the plastic container has a length of 5 - 30 mm. This improves the thickness uniformity of the film. In the first apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the thermal catalyst is positioned such that the upper end thereof is placed at 10 ~ 30 mm below the lower end of the portion of nozzle of the plastic container. This is possible to control the deformation of the support portion of the plastic container. In the first apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the inner surface of the vacuum chamber is black or the inner surface has a surface hardness (Rmax) of 0.5 μm or more. , and the cooling medium is provided inside or outside the chamber. By controlling the reflection of the emission light generated by the thermal catalyst, it is possible to reduce the thermal effects inflicted on the plastic container. The first apparatus for manufacturing a gas barrier plastic container according to the present invention preferably has a cooling medium from which a cooled liquid or gas is applied to the outer surface of the plastic container. This makes it possible to reduce the thermal effects inflicted on the plastic container. The second apparatus for manufacturing a gas barrier plastic container according to the present invention comprises a vacuum chamber for housing a plastic container, a discharge pump evacuating the vacuum chamber, a thermal catalyst placed on the periphery of the plastic container , a source gas supply pipe that supplies a source gas in the outer space of the plastic container to the interior of the vacuum chamber, and a supply of heating energy that supplies electricity to the thermal catalyst to generate heat. The present manufacturing apparatus is an apparatus for manufacturing a gas barrier plastic container in which a thin film of reality is formed on the outer surface of the container. In the second apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the thermal catalyst is plurally placed in rotationally symmetrical positions with respect to the main axis of the plastic container, or is configured to spirally wind with the main axis of the plastic container in the center, or is configured to wind respectively in parallel to a plurality of transversal cuts of the main axis of the plastic container. This improves the thickness uniformity of the film. In the second apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the thermal catalysts are reciprocally placed 5 cm or more apart. This facilitates obtaining a high production efficiency for the chemical species and for the uniformity of the thickness of the film without inflicting thermal damage to the plastic container. In the second apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the thermal catalyst is positioned in such a way that the distance to the outer surface of the plastic container is fixed. This improves the uniformity of the thickness of the film on the outer surface including the bottom of the container. The second apparatus for manufacturing a gas barrier plastic container according to the present invention preferably has a container cooling medium which applies a cooled household liquid to the inner surface of the plastic container. This makes it possible to reduce the thermal effects inflicted on the plastic container. In the first or second apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the thermal catalyst is placed at least in the outlet part of the gas ejection orifice of the source gas supply line. This makes it possible to effectively activate the source gas by the thermal catalyst. In the first or second apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the source gas supply line is provided with a housing mechanism for housing the thermal catalyst inside. For example, there are cases where chemical reactions occur between the thermal catalyst and a portion of the source gas when there is no film formation, and in the case where this kind of source gas is used, it is possible to extend the life of the thermal catalyst. In the first or second apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the thermal catalyst is placed inside the source gas supply line. Because the distance between the thermal catalyst and the surface of the plastic container may be greater, it is possible to reduce the thermal effects inflicted on the plastic container. In the first or second apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the thermal catalyst has a portion in which a wire is processed to form a helical spring, a wavy line shape or a shape of zigzag line. This makes it possible to increase the opportunity for contact between the source gas and the thermal catalyst, and as a result, increases the reaction efficiency.

In the first or second apparatus for manufacturing a gas barrier plastic container according to the present invention, preferably the thermal catalyst is placed along the direction of ejection of the source gas. This makes it possible to increase the opportunity for contact between the source gas and the thermal catalyst, and as a result, the reaction efficiency increases. The first method for manufacturing a gas barrier plastic container according to the present invention comprises a process in which the interior of a vacuum chamber that houses a plastic container is discharged to form a pre-set pressure, and a process in which a state of electricity supply is maintained to a thermal catalyst placed inside the vacuum chamber to generate heat above a pre-established temperature, a source gas is introduced into the thermal catalyst to decompose the source gas and create the chemical species, whereby a thin gas barrier film is formed by the chemical species reaching at least some of the inner surface or outer surface of the plastic container. The present manufacturing method is a method for manufacturing a gas barrier plastic container in which a thin gas barrier film is formed on the interior surface of the container.

In the first method for manufacturing a gas barrier plastic container according to the present invention, the injection of the source gas is preferably completed after the thermal catalyst temperature increase above the pre-set temperature. The pre-set temperature is determined according to the combination of the catalyst and the source gas, and according to the characteristics of the thin film formed, but in the case where the film formation is carried out using a tungsten catalyst and a Silicon gas, for example, the temperature of the tungsten catalyst is set at 1600 ° C or more. From the beginning of the formation of the film, it is possible to create the chemical species sufficiently activated by the thermal catalyst, and it facilitates the obtaining of a film having good gas barrier properties. The second method for manufacturing a gas barrier plastic container according to the present invention comprises a process in which after at least one of the interior or exterior spaces of a plastic container housed in a reaction chamber is filled with a source gas under a preset pressure, the supply of the source gas is stopped to stop the incoming and outgoing flow of the gas in the reaction chamber, and a process in which a state of supply of electricity to a thermal catalyst is maintained to generate heat above a pre-set temperature, the thermal catalyst is guided into the space filled with the source gas in order to decompose the source gas and create the chemical species, whereby a film of gas barrier delegate is formed by the species chemicals that reach at least some of the inner surface or outer surface of the plastic container. The present method of manufacture is a method for manufacturing a gas barrier plastic container in which a thin gas barrier film is formed on the outer surface of the container. In the plastic gas barrier vessel according to the present invention, a thin film of hydrogen-containing SiNx, a thin film of DLC containing hydrogen, a thin film of hydrogen-containing SiOx or a thin film is formed. of SiCxNy with hydrogen content as a thin gas barrier film on at least one of the inner surface or the outer surface of a plastic container, and having the SiNx thin film with hydrogen content, the thin film of DLC with hydrogen content, the SiOx thin film with hydrogen content or the SiCxNy thin film with hydrogen content has a film thickness of 5 ~ 100 nm and a hydrogen content ratio of 1 ~ 10 atomic%. In the apparatus for manufacturing a gas barrier plastic container, the present invention satisfies the condition that it is possible to use the same vacuum chamber as when the container forms are different, provided that the energy source is not necessary. high frequency, and the condition that the formation of the film for a plurality of containers within a vacuum chamber can be carried out in order to decrease the cost of the apparatus. In this regard, it is possible to form a thin gas barrier film on the inner surface or outer surface of the plastic container. Furthermore, in the method for manufacturing a gas barrier plastic container, the present invention makes it possible to form a thin gas barrier film which is not damaged by the plasma on at least some of the inner surface or outer surface of the container plastic. Furthermore, in the gas barrier plastic container, the present invention makes it possible to impart so much durability which makes it difficult for cracks to be generated even when there is formation or contraction of the container as well as good gas barrier properties for the oxygen gas and the gas. carbon dioxide.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic drawing showing an embodiment of the apparatus for manufacturing a plastic gas barrier vessel according to the first embodiment, where (a) is the case where the thermal catalyst has a linear shape, ( b) is the case where the thermal catalyst has the form of a helical spring, and (c) it is the case where the thermal catalyst has the form of a zigzag line. Figure 2 is a schematic drawing showing another embodiment of the apparatus for manufacturing a plastic gas barrier vessel according to the first embodiment, where (a) is the case where the thermal catalyst has the form of an inverted letter M, (b) it is the case where the thermal catalyst has the form of a helical spring, and (c) it is the case where the thermal catalyst has the form of a zigzag line. Figure 3 is a schematic drawing showing one embodiment of the apparatus for manufacturing a plastic gas barrier vessel according to the second embodiment, where (a) is the case where the thermal catalyst has a linear shape, and (b) is the case where the thermal catalyst has the form of a helical spring.

Figure 4 shows a cross-sectional view taken along line A-A '. Figure 5 shows a cross-sectional view taken along line A-A '. Figure 6 is a conceptual drawing of an apparatus for forming a thin gas barrier film simultaneously on the inner surface of a plurality of plastic containers. Figure 7 is a conceptual drawing of an apparatus for forming a thin gas barrier film simultaneously on the outer surface of a plurality of plastic containers. Figure 8 is a conceptual drawing of an apparatus for forming a thin gas barrier film simultaneously on the outer surface of a plurality of in-line plastic containers. Figure 9 is a structural drawing of a prior art DLC film forming apparatus. Figure 10 shows another embodiment of the positional relationship of the thermal catalyst and the source gas supply line. Figure 11 is a conceptual drawing for describing the container cooling medium, where (a) is the case when the formation of the film is carried out on the inner surface of the plastic container, and (b) is the case when the Film formation is carried out on the outer surface of the plastic container. Figure 12 shows another embodiment of the thin film forming chamber of Figure 8.

DETAILED DESCRIPTION OF THE INVENTION The present invention described in detail below with reference to the preferred embodiments, should not be construed as that the present invention is limited to these descriptions. A plasma CVD film forming apparatus according to the present embodiments is described with reference to Figures 1-12. In addition, the same symbols are applied to the same portions / parts. First, a description of an apparatus for manufacturing a gas barrier plastic container according to the first embodiment of which makes it possible to form a thin gas barrier film on the interior surface of a container. Figure 1 is a schematic drawing showing an embodiment of the apparatus for manufacturing a plastic gas barrier vessel according to the first embodiment, where (a) is the case where the thermal catalyst has a linear shape, (b) is the case wherein the thermal catalyst has the form of a helical spring, and (c) is the case where the thermal catalyst has the form of a zigzag line. However, Figures 1 (b) (c) are partial enlarged views of a source gas supply pipe 23. In addition, unless explicitly specified otherwise, "Figure 1" is described as "Figure 1 (FIG. a) "below. An apparatus 100 for manufacturing a gas barrier plastic container shown in Figure 1 has a vacuum chamber 6 for housing a plastic container 11., a discharge pump (not shown in the drawings) evacuating the vacuum chamber 6, a source gas supply pipe 23 formed from an insulating and heat resistant material that is configured to be inserted into and removed from the interior of the container plastic 11 in order to supply a source to the interior of the plastic container 11, a thermal catalyst 18 which is supported on the source gas supply pipe 23, and a heating energy supply 20 which supplies electricity for heating the thermal catalyst 18. In the vacuum chamber 6, a space is formed to house the plastic container 11 inside, and this space forms a reaction chamber 12 for the formation of the thin film. The vacuum chamber 6 is constructed from a lower chamber 13 and an upper chamber 15 which is installed to freely connect and disconnect from the upper portion of the lower chamber 13 and seal the interior of the lower chamber 13 by a gasket type 14. In the upper chamber 15 there is an ascending-descending drive mechanism not shown in the drawings, and moves up and down according to the loading and unloading of the plastic container 11. The space within the lower chamber 13 it is formed slightly larger than the external shape of the plastic container 11 housed therein. This plastic container 11 is a beverage bottle, but it can be a container used for other uses. Within the vacuum chamber 6, particularly inside the lower chamber 13, preferably the inner surface 28 forms a black inner wall to the lower surface has a surface hardness (Rmax) of 0.5 μm or greater in order to avoid reflection of the light emitted in accordance with the heating of the thermal catalyst 18. The surface hardness (Rmax) is measured using a surface hardness measuring device (DE TAX3 manufactured by ULVAC TECHNO (Ltd.)), for example. In order to make the inner surface 28 an internal measurement wall, there is a coating treatment such as black nickel coating or black chromium coating or the like, a chemical conversion coating treatment such as a RAYDENT or a coating finish. black oxide or similar, or a coloring method in which a black paint is applied. In addition, the cooling medium 29 such as a cooling pipe through which the cooling water or the like flows is preferably provided to the interior (not shown in the drawings) or to the exterior (Figure 1) of the chamber at vacuum 6 to prevent the lower bed 13 from increasing its temperature. The reason why the lower chamber 13 in the vacuum chamber 6 is particularly cooled is that, when the thermal catalyst 18 is inserted into the plastic container 11, the thermal catalyst 18 is housed just in the space inside the lower chamber 13. By avoiding reflection of the light and cooling the chamber to vacuum 6, it is possible to control the temperature increases of the plastic container 11 and the resulting thermal deformation. Further, when a chamber 30 made of a transparent body such as a glass chamber, for example, can allow the passage of the emission light generated by the thermal catalyst 18 supplied with electricity, it is placed inside the lower chamber 13, because the temperature of the glass chamber touching the plastic container 11 increases slowly, it is possible to further reduce the thermal effects inflicted on the plastic container 11.

The source gas supply pipe 23 is supported so as to hang in the center of the inner roof surface of the upper chamber 15. A source gas flows into the source gas supply pipe 23 via flow controllers of 24a ~ 24c and valves 25a ~ 25d. The source gas supply pipe 23 preferably has a cooling pipe formed as an integral body. The structure of this kind of source gas supply pipe 23 is, for example, a double pipe structure. In the source gas supply pipe 23, the inner pipe of the double pipe forms a source gas channel 17, in which one end is connected to a gas supply port 16 provided in the upper chamber 15, and the other end forms a 17x gas ejection hole. In this manner, the source gas is discharged from the gas ejection port 17x at the tip of the source gas channel 17 connected to the gas supply port 16. On the other hand, the outer pipe of the double pipe is a water channel of cooling 27 to cool the source gas supply pipe 23, and act as a cooling pipe. Further, when the thermal catalyst 18 is supplied with electricity to generate heat, the temperature of the source gas channel 17 increases. In order to avoid this, cooling water is circulated in the cooling water channel 27. Particularly in one end of the cooling water channel 27, the cooling water is supplied from the cooling water supply means not shown in the drawings connected in the upper chamber 15, and at the same time the cooling water which has finished the Cooling returns to the cooling water supply medium. On the other hand, the other end of the cooling water channel 27 is sealed near the gas ejection port 17x, and here the cooling water is returned. All the source gas supply pipe 23 is cooled by the cooling water channel 27. Upon cooling, it is possible to reduce the thermal effects inflicted on the plastic container 11. According to the above, the material of the supply pipeline of source gas 23 is preferably an insulating material having a high thermal conductivity. For example, it is preferably a ceramic pipe formed from a material in which the aluminum nitride, silicon carbide, silicon nitride, an aluminum oxide formal component, a metal pipe whose surface is coated with a material in the that the aluminum nitride, silicon carbide, silicon nitride an aluminum oxide formal main component. It is possible to provide electricity in a stable manner to the thermal catalyst, it has durability, and it is possible to discharge the heat efficiently by the thermal conduction of the heat generated by the thermal catalyst. The source gas supply pipe 23 may be formed as another embodiment not shown in the drawings in the following manner. Particularly, the source gas supply pipe forms a double pipe, the outer pipe forms a source gas channel, and a hole, preferably a plurality of holes are formed in the side wall of the outer pipe. On the other hand, the inner pipe of the double pipe of the source gas supply pipe is formed by a thin pipe which forms a cooling water channel through which the cooling water flows. The thermal catalyst is wired along the side wall of the source gas supply pipe, and the source gas passing through the holes provided in the side wall of the outer pipe makes contact with the thermal catalyst portion throughout from the side wall, and this makes it possible to create a chemical species effectively. If the gas ejection port 17x is too far from the bottom of the plastic container 11, it is difficult to form a thin film inside the plastic container 11. In the present embodiment, the length of the source gas supply pipe 23 is preferably formed such that the distance Ll from the ejection hole 17x to the bottom of the plastic container 11 is 5 ~ 30 mm. This improves the uniformity of the thin film. At a distance of 5 ~ 30 mm, it is possible to form a uniform thin film on the inner surface of the plastic container 11. If the distance is greater than 30 mm, it becomes difficult to form a thin film on the bottom of the plastic container 11, and if the distance is less than 5 mm, it becomes difficult to discharge the source gas. This fact can also be understood theoretically. In the case of a 500 ml container, the diameter of the container body is 6.4 cm, and from the mean free path? = 0.68 / Pa [cm] in the air at room temperature, the molecular flow is observed at a pressure <; 0.106 Pa, the viscous flow is a pressure > 10.6 Pa, and the intermediate flow 0.106 Pa < pressure < 10.6 Pa. At a gas pressure of 5 - 100 Pa at the time of formation of the film, the flow of already a viscous flow is formed, and optimal conditions are formed at the distance between the gas direction orifice 17x and the bottom of the plastic container 11. The thermal catalyst 18 improves the decomposition of the source gas in a catalytic chemical vapor waste method. In the present embodiment, the thermal catalyst 18 is preferably constructed from a material that includes one or two or more metallic elements selected from the group of C, W, Ta, Ti, Hf, V, Cr, Mo, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt. Having electrical conductivity, it is possible to generate heat by itself when supplying electricity. The thermal catalyst 18 assumes a wiring form, and one end of the thermal catalyst 18 is connected to a connector portion 26a that forms a connection point between the thermal catalyst 18 and a wiring 19 provided in the source gas supply pipe 23 below of a fixed point in the upper chamber 15. Furthermore, it is supported by an insulating ceramic member 35 provided in the gas ejection port 17x which is the tip portion. In addition, the other end of the thermal catalyst 18 is bent back and connected to a connector portion 26b. In this way, because the thermal catalyst 18 is supported along the lateral surface of the source gas supply pipe 23, it is configured to be placed approximately on the main axis of the space within the lower chamber 13. Figure 1 (a) shows the case when the thermal catalyst 18 is placed along the periphery of the source gas supply pipe 23 in order to be parallel to the axis of the source gas supply pipe 23, but with the connecting portion 26a as a starting point, it can be wound spirally around the lateral surface of the source gas supply pipe 23, and then supported by the insulating ceramic 35 fixed near the gas ejection port 17x, bent backwards and return to connector portion 26b. Here, the thermal catalyst 18 is attached to the source gas supply pipe 23 suspended over the insulating ceramic 35. Figure 1 (a) shows the case when the thermal catalyst 18 is placed near the gas ejection port 17x of the supply gas supply pipe 23 on the outside of the gas ejection hole 17x. In this way, because it is easy for the source gas discharged from the gas ejection port 17x to make contact with the thermal catalyst 18, the source gas can be effectively activated. Here, the thermal catalyst 18 is preferably positioned to separate slightly from the side surface of the source gas supply pipe 23. This is to moderate the sudden temperature increases of the source gas supply pipe 23. In addition, it is possible to increase the opportunity for contact between the source gas discharged from the gas ejection port 17x and the source gas in the reaction chamber 12. The outside diameter of the source gas supply pipe 23 including the thermal catalyst 18 needs to be smaller than the inner diameter of a nozzle portion 21 of the plastic container. This is because the source gas supply pipe 23 that includes the thermal catalyst 18 is inserted from the nozzle portion 21 of the plastic container. Accordingly, when the thermal catalyst 18 is separated beyond the necessary surface of the source gas supply pipe 23, the thermal catalyst 18 is easier to contact the nozzle portion 21 of the plastic container when the supply gas supply pipe 23 is inserted from the nozzle portion 21 of the plastic container. The width of the thermal catalyst 18 is conveniently greater than 10 mm and less than (the inner diameter of the nozzle portion 21-6 mm) when changes in position are considered at the time of insertion from the nozzle portion 21 of the plastic container. Here, the inner diameter of the nozzle portion 21 is approximately 21.7 D 39.8 mm. The maximum temperature when heating the thermal catalyst 18 is preferably less than the temperature at which the thermal catalyst softens. The maximum temperature is different depending on the material of the thermal catalyst, but is preferably 2100 ° C when it is tungsten, for example. Further, when the thermal catalyst 18 is tungsten, the operating temperature of the thermal catalyst is preferably 1600 D 2100 ° C. In addition, the thermal catalyst 18 preferably has a portion in which a wire is processed to obtain a helical spring shape as seen in Figure 1 (b) in order to increase the opportunity to contact the source gas. The helical spring shape is not limited to a cylindrical shape, and includes a conical shape, a barrel shape or an hourglass shape, and includes irregular separation shapes in which the spacing between these windings changes. In addition, it can have a portion in which the wire is processed to obtain a zigzag line shape as seen in Figure 1 (c).

Alternatively, it may have a portion in which the wire is processed to obtain a wavy line shape (not shown in the drawings). In either of these forms, the thermal catalyst 18 is preferably positioned along the ejection direction of the source gas. In this way, the opportunity for the source gas 33 to make contact with the thermal catalyst 18 is increased. With respect to the method for fixing the thermal catalyst 18 to the source gas supply pipe 23, the following may be provided as another embodiment shown in the drawings. Particularly, the source gas supply pipe is formed as a double pipe, where the outer pipe is formed by a porous pipe having a porosity of 10 D 40% which forms a source gas channel. The thermal catalyst can be wound directly around this porous outer pipe. The fixing stability of the thermal catalyst is improved, and because the source gas is emitted both from the gas ejection port and from the side wall of the outer pipe, the contact efficiency with the thermal catalyst is improved. In this case, the inner pipe of the double pipe of the source gas supply pipe is formed by a thin pipe forming a cooling water channel through which the cooling water flows. Figure 10 shows another embodiment of the positional relationship of the thermal catalyst 18 and the source gas supply pipe 23. In Figure 10, the thermal catalyst 18 is placed inside the source gas supply pipe 23. The catalyst Thermal 18 is placed in two rows along the ejection direction of the source gas 33. In this way, the opportunity for the source gas 33 to contact the thermal catalyst 18 is increased. Also, because the thermal catalyst it is placed inside the source gas supply pipe, the distance between the thermal catalyst and the surface of the plastic container can be made larger, and this makes it possible to control the generation of thermal deformations of the plastic container. As seen in Figure 10, the thermal catalysts 18a, 18b are preferably positioned in such a way that the respective wire portions are oriented in different directions. In Figure 10, the wires are in a reciprocally different vertical and horizontal relationship. In addition, the cross-sectional shape of a pipe of the source gas supply pipe 23 is a square in Figure 10, but it can be a circle, an ellipse or a rectangle. Further, if the insert from the nozzle portion of the plastic container is carried out to form a film on the inner surface of the plastic container, the diameter of the pipe needs to be smaller than the diameter of the nozzle portion. On the other hand, in the case where a film is formed on the outer surface of the plastic container, the diameter of the pipe preferably becomes larger in order to expand the gas flow rate. The heating energy supply 20 is connected to the thermal catalyst 18 through the connector portions 26a, 26b and the wiring 19. When electricity is applied to the thermal catalyst 18 with the heating energy supply 20, the thermal catalyst 18 generates heat. In addition, because the flexibility ratio is relatively small at the time the plastic container 11 is formed from the nozzle portion 21 of the plastic container to the container support, when heat catalyst 18 generating high temperature heat is placed nearby. , the deformation is due to the fact that heat is easily generated. According to the experiments, if the positions of the connecting portions 26a, 26b at the points of connection with the wiring 19 and the thermal catalyst 18 were not more than 10 mm apart from the lower end of the nozzle portion 21 of the plastic container, the portions of the support of the plastic container 11 underwent a thermal deformation, and if they were more than 30 mm apart, it was difficult to form a thin film on portions of the support of the plastic container 11. In this regard, the thermal catalyst 18 is preferably placed Such that the upper end thereof is placed 10 D 30 mm below the lower end of the nozzle portion 21 of the plastic container. Namely, the distance L2 between the connecting portions 26a, 26b and the lower end of the nozzle portion 21 is preferably 10 D 30 mm. This makes it possible to control the thermal deformation of the support portion of the container. In addition, a discharge pipe 22 communicates with the space inside the upper chamber 15 through a vacuum valve 8, and the air in the reaction chamber. 12 inside the vacuum chamber 6 is discharged by a discharge pump not shown in the drawings. Figure 2 is a schematic drawing showing another embodiment of the apparatus for manufacturing a plastic gas barrier vessel according to the first embodiment, where (a) is the case where the thermal catalyst has the form of an inverted letter M, (b) it is the case where the thermal catalyst has the form of a helical spring, and (c) it is the case where the thermal catalyst has the form of a zigzag line. However, Figures 2 (b) (c) are partial enlarged views of a source gas supply pipe 23. In addition, unless otherwise explicitly specified, "Figure 2" is described as the "Figure 2". 2 (a) "shown below. An apparatus 200 for manufacturing a gas barrier plastic container shows the case where the source gas supply pipe 23 is formed having a triple pipe structure. The interior pipe of the triple pipe forms a source gas channel 17a through which a source gas 33a flows through a gas supply port 16a. The wiring 19 is placed along the part of the interior surface or the interior or part of the exterior surface of the source gas channel 17a that the interior pipe of the triple pipe so as to remain parallel to the main axis of the pipe. same. At the tip of the source gas channel 17a, the thermal catalyst 18 is placed in the outlet portion of the source gas ejection port 17x in a position contacting the discharged source gas 33a. Particularly, in the apparatus 200 for manufacturing a plastic gas barrier vessel, the thermal catalyst 18 is not placed on the side surface of the source gas supply line 23, and is placed only in the outlet part of the ejection orifice. of gas 17x. In addition, the thermal catalyst 18 is connected to the connector portions 26a, 26b provided at the end of the wiring 19. The intermediate pipe of the triple pipe forms the cooling water channel 27 through which the cooling water flows. The outer pipe of the triple pipe forms a source gas channel 17b through which a source gas 33b flows through a gas supply port 16b. This mode is suitable when the source gases 33a, 33b flowing respectively through the inner pipe and the outer pipe are different kinds of gases. The source gases 33a, 33b can be mixed together in the outlet portion of the gas ejection port 17x of the source gas supply line 23. The triple line is preferably formed from an insulating ceramic. Here, in the case where a portion of the case in which it undergoes a chemical reaction with the thermal catalyst 18 below 1590 ° C, the apparatus 200 for manufacturing a plastic gas barrier vessel makes it possible to avoid such a chemical reaction. For example, in the case where the thermal catalyst 18 is tungsten and a portion of the source gas is silicon tetrahydride. (silane), when the tungsten is below 1590 ° C, both will undergo chemical reactions, and the electrical resistance of the thermal catalyst 18 will end up decreasing. For this reason, in order to avoid contact between the source gas 33b and the thermal catalyst 18 below 1590 ° C, a mechanism for housing the thermal catalyst 18 is preferably provided within the source gas supply pipe 23. Particularly , in order to change the relative positions of the inner pipe, the intermediate pipe and the outer pipe with respect to the axial direction of the triple pipe to make it possible for the tip of the inner pipe where the heat catalyst 18 is placed to be inserted and Extract from the intermediate pipe and the outer pipe, a telescopic mechanism is provided to the inner pipe, a telescopic mechanism for the intermediate pipe and the outer pipe between the upper chamber 15 and the triple pipe. The telescopic mechanism can be, for example, a bellows. In this way, the life of the thermal catalyst 18 can be extended. When electricity is supplied to the thermal catalyst 18, the thermal catalyst 18 generates heat. After that, the inner pipe of the triple pipe is extended. Then, the thermal catalyst 18 placed on the tip of the source gas channel 17a protrudes from the interior of the source gas supply pipe 23, and the thermal catalyst 18 strives to make contact simultaneously with both gases, the source gas 33a and the gas source 33b. Even when the thermal catalyst 18 reaches an elevated temperature, because the source gas 33b is reducing the ammonia gas (NH3), a chemical reaction does not occur when the contact is made. In addition, the thermal catalyst 18 preferably has a portion in which a wire is processed to obtain a helical spring shape as seen in Figure 2 (b) in order to increase the opportunity to contact the source gas. The helical spring shape is not limited to a cylindrical shape, and includes a conical shape, a barrel shape an hourglass shape, and includes irregular separation shapes in which the spacing between these windings changes. In addition, it may have a portion in which the wire is processed to obtain a zigzag line shape as seen in Figure 2 (c). Alternatively, it may have a portion in which it is processed from it to obtain a wavy line shape (not shown in the drawings). In either of these forms, the thermal catalyst 18 is preferably positioned along the ejection direction of the discharge gas. For example, a plural configuration of the thermal catalyst 18 can be formed, or a vector component is assigned to the thermal catalyst 18 in the ejection direction of the source gas. In this way, the opportunity is increased for the case in which it makes contact with the thermal catalyst. Further, in the case where a delegated DLC film is formed, for example, in the case where the source gas is a source gas formed from hydrogen and carbon such as methane gas or acetylene gas, the thermal catalyst 18 will not experience a chemical reaction with the source gas. In this case, in the manufacturing apparatus of Figure 2, the thermal catalyst 18 can be fixed in the state where it is housed within the source gas supply pipe 23 with or the thermal catalyst 18 can be fixed in the state where it protrudes of the source gas supply pipe 23, without providing the telescopic mechanism. The container according to the present invention includes a container that uses a cover or a stopper or seals, or a container used in an open state that does not use these. The size of the opening is determined according to the content. The plastic container includes a plastic container having a moderate stiffness and a certain thickness, and a plastic container formed from a laminated material that has no rigidity. The substance with which the plastic container is filled according to the present invention can be a beverage such as a carbonated beverage, a fruit juice drink or a soft drink or the like. In addition, the container can be a returnable container a disposable container. The resin used during the formation of the plastic container 11 of the present invention may be polyethylene terephthalate resin (PET), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin (PP-polypropylene), cycloolefin copolymer resin (COC - ring olefin copolymer), ionomer resin, poly-4-methylpenten-l resin, polymethyl methacrylate resin, polystyrene resin, ethylene-vinyl alcohol copolymer resin, acrylonitrile resin , polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, polyamide-imide resin, polyacetal resin, polycarbonate resin, polysulfone resin, or ethylene tetrafluoro resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin. Of these, PET is particularly preferred. In the apparatus for manufacturing a gas barrier plastic container according to the first embodiment, the gas source is conveniently selected from the known source gases used by the CVD method in accordance with the type of thin film target. gas barrier. Because the apparatus for manufacturing a gas barrier plastic container and the method for manufacturing the container according to the present invention can form various thin films such as inorganic films, organic films and the like, the conceptual scope of the manufacturing apparatus and the manufacturing method should not be interpreted based on the type of source gas used. The source gas for a thin film of carbon can be an alkane gas such as methane, ethane, propane, butane, pentane, hexane or the like, an alkane gas such as ethylene, propylene, butane or the like, an alkadiene gas such as butadiene, pentadiene or the like, an alkyne gas such as acetylene, methyl acetylene or the like, an aromatic hydrocarbon gas such as benzene, toluene, xylene, indene, naphthalene, phenanthrene or the like, a cycloalkane gas such as cyclopropane, cyclohexane or the like, a cycloalkene gas such as cyclopentene, cyclohexene or the like, an alcohol gas such as methanol, ethanol or the like, a ketone gas such as acetone, methyl ethyl ketone or the like, or an aldehyde gas such as formaldehyde, acetaldehyde or the like, for example. The source gas for a thin film of silicon can be dimethoxy (methyl) silane, ethoxy dimethyl silane, dimethoxy dimethyl silane, trimethoxy methyl silane, tetramethoxy silane, tetramethyl silane, dimethoxy methyl silane, ethoxy trimethyl silane, diethyloxy methyl silane, ethoxy dimethyl vinyl silane, allyl trimethyl silane, diethyloxy dimethyl silane, tolyl ethyl silane, hexamethylene disiloxane, hexamethyl disilane, vinyl silane diethyloxy methyl, triethoxy methyl silane, triethoxy vinyl silane, bis (trimethyl silyl) acetylene, tetraethoxy silane, trimethoxy phenyl silane, methyl-glycidoxy propyl (dimethoxy) silane, silane methyl-propyl (trimethoxy) of? -glycidoxy, propyl methyl (dimethoxy) methyl-methacryloxy silane, methyl silane propyl (trimethoxy) -methacryloxy, diphenyl silane dihydroxy, diphenyl silane, phenyl silane from trietoxi, s tetraisopropoxy ilane, tetra-n-butoxy silane, tetraphenoxy silane, or poly (methyl hydrogen siloxane), for example. Among them, the source gas for a thin film of Si-CN may be an amino silicon compound such as dimethyl amino silane tetrakis, tris dimethyl amino silane, bis dimethyl amino silane, dimethyl amino silane or similar, for example. The source gas for a Si-C thin film can be a dialkyl silicon compound such as dimethyl silane, monomethyl silane, trimethyl silane, tetramethyl silane, monomethyl silane, diethyl silane, triethyl silane, silane of tetraethyl or the like, for example. The source gas for a thin film of Si-C-0 may be an alkoxy silicon compound such as tetraethoxy silane, dimethyl dimethoxy silane, dimethyl hetose methoxy trisilane or the like. These source gases can be used individually or together to form a thin film of SiNx containing hydrogen, a thin film of DLC containing hydrogen, a thin film of SiOx containing hydrogen, a thin film of SiCxNy with hydrogen content as a thin film gas barrier. further, it is possible to improve the film quality of the gas barrier thin film by introducing a gas such as hydrogen, oxygen, nitrogen, steam, ammonia or CF4 which does not polymerize but participates in the chemical reactions in the gas source towards the reaction chamber 12 where there is the heat generation thermal catalyst 18. For example, in the case where a thin film of silicon nitride is formed, silane, ammonia and hydrogen are combined to form a source gas. The source gas and a dilution gas can be shown together. For example, an inert gas such as argon or helium or the like is inactive in chemical reactions at the time of film formation, and can be used to adjust the concentration of the source gas and adjust the pressure inside the chamber to empty. Next, a description will be provided of an apparatus for manufacturing a gas barrier plastic container according to the second embodiment, which makes it possible to form a thin gas barrier film on the outer surface of a container. Figure 3 is a schematic drawing showing one embodiment of the apparatus for manufacturing a plastic gas barrier vessel according to the second embodiment, wherein (a) is the case where the thermal catalyst has a linear form, and (b) ) is the case where the thermal catalyst has the form of a helical spring. However, Figure 3 (b) is a schematic drawing of the thermal catalyst. In addition, unless explicitly specified otherwise, "Figure 3" is described as "Figure 3 (s)" shown below. An apparatus 300 for manufacturing a plastic gas barrier vessel shown in Figure 3 has a vacuum chamber 60 for housing a plastic container 11, a discharge pump (not shown in the drawings) evacuating the vacuum chamber 60, a thermal catalyst 18 that is placed on the periphery of the plastic container 11, a source gas pipe 31 that supplies a source gas to the space outside the plastic container 11 to the interior of the vacuum chamber 60, and a heating energy supply 20 which supplies electricity for heating the thermal catalyst 18. In the apparatus 300 for manufacturing a gas barrier plastic container, the nozzle portion of the plastic container 11 is fixed by a rotary bottle mechanism 32, and the plastic container 11 is placed such that it does not touch the inside of the vacuum chamber 60. In the vacuum chamber 60, a space is formed to house the plastic container 11 inside, and this Acium forms a reaction chamber 12 for the formation of thin films. The vacuum chamber 60 is constructed from a lower chamber 63 and an upper chamber 65 which is installed in order to freely connect and disconnect from the upper portion of the lower chamber 63 and seal the interior of the lower chamber 63 for a O-type seal 14. In the upper chamber 65 there is an ascending-descending drive mechanism not shown in the drawings, and it moves up and down in accordance with the loading and unloading of the plastic container 11. The space within the chamber lower 63 is formed to be larger than the outer shape of plastic container 11 in order to make it possible for thermal catalyst 18 to be placed on the periphery of plastic container 11 housed therein. Here, one end of the thermal catalyst 18 is connected to a connecting portion 79a which is the connection point between the wiring 19 and the thermal catalyst 18. Furthermore, in the manufacturing apparatus of Figure 3, with the connecting portion 79a as the point Initially, the thermal catalyst 18 is placed in a linear state from a side surface to the interior of the lower chamber 63 through the lower surface to the facing side surface, bends back from there, and is once again placed in a linear state towards the lateral surface facing, the lower surface and the inner side surface, and the other end are connected to a connector portion 79b. In order to show the positional relationship between the thermal catalyst 18 and the plastic container 11 at this time, a cross-sectional view taken along the line A-A 'is shown in Figure 4. The thermal catalyst 18 and the plastic container 11 are configured with a left and right equidistant spacing in the drawing. The thermal catalyst 18 is positioned such that the distance to the outer surface of the plastic container 11 is fixed. This improves the uniformity of the thickness of the film on the outer surface including the bottom of the container. In addition, two or more thermal catalysts 18 can be placed. In this case, the thermal catalyst 18 is preferably placed plurally in rotationally symmetrical positions with respect to the main axis of the plastic container. In order to show the positional relationship between the thermal catalyst 18 and the plastic container 11 in the case where two thermal catalysts 18 are placed, a cross-sectional view taken along the line A-A 'is shown in Figure 5. The thermal catalyst 18 and the plastic container 11 are placed with an equidistant top, bottom, left and right spacing in the drawing. In any case shown in Figure 4 or Figure 5, in carrying out the formation of the film while rotating the plastic container 11 with the main shaft in the center by the rotary bottle mechanism 32, it is possible to improve the uniformity of the formation of the movie. In particular, in the case of Figure 4, because there is a thermal catalyst 18, the effect of the improvement in uniformity of film formation is high. Although not shown in the drawings, as another embodiment of the configuration of the thermal catalyst 18, there is a manner in which it spirals around the periphery of the plastic container 11 with the main axis of the plastic container 11 in the center, or there is one embodiment in which a plurality of annular thermal catalysts are configured in parallel as they are respectively wound in parallel on a plurality of cross-sections of the main axis of the plastic container 11. In any embodiment, it is possible to improve the uniformity of the thickness of the film. Of course, in this embodiment as well, the formation of the film can be performed while the plastic container 11 rotates with the main axis at the center by the rotary bottle mechanism 32. Here, in the case where there is a plural configuration of thermal catalysts 18 , they are preferably placed separately from each other by 5 cm or more. This makes it easier to obtain a high production efficiency for the chemical species and the uniformity of the thickness of the film without inflicting thermal damage to the plastic container. The material of the thermal catalyst 18 may be the same as that of the first embodiment. In addition, the thermal catalyst 18 preferably has a portion in which a wire is processed to obtain a helical spring shape as seen in Figure 3 (b) in order to increase the opportunity for contact with the source gas. The helical spring shape is not limited to a cylindrical shape, and includes a conical shape, a barrel shape or an hourglass shape, and includes irregular separation shapes in which the spacing between these windings changes. In addition, it may have a portion in which the wire is processed to obtain a zigzag line shape (not shown in the drawings). Alternatively, it may have a portion in which the wire is processed to obtain a wavy line shape (not shown in the drawings). In either of these forms, the thermal catalyst 18 is preferably positioned along the ejection direction of the source gas. For example, a plural configuration of the thermal catalyst 18 may be formed., or a vector component can be assigned to the thermal catalyst 18 in the ejection direction of the source gas. In this way, the opportunity for the source gas to contact the thermal catalyst is increased. One end of the source gas pipe 31 is connected to a supply port 66 provided on the lower surface of the lower chamber 63. A source gas supply pipe 73 is connected to the other end of the gas pipe 31 and an intermediate derivation of it. In Figure 3, a plurality of source gas supply pipes 73 are provided, and each has a gas ejection port 77x provided at the tip thereof. A source gas 33 flows into the source gas supply pipes 73 via the source gas supply line 31, the gas supply port 66, the flow controllers 24a ~ 24c and the valves 25a ~ 25d. In this way, the source gas 33 is discharged through the gas ejection holes 77x. All the gas ejection holes 77x are directed towards the outer surface of the plastic container 11, and the source gas can be discharged to any part of the outer surface thereof. In addition, the thermal catalyst 18 is placed in the outlet part of the gas ejection holes 77x. In this way, because the contact between the thermal catalyst 18 and the source gas occurs frequently, it is possible to increase the yield of the chemical species. The source gas supply pipe 73 is a single pipe made of metal. It can be formed as a double pipe in order to make the cooling water flow in the same way as in the case of the first mode. In addition, it can be formed as a ceramic pipe or a metal pipe in which the surface of a ceramic material discovered in the same manner as in the case of the first embodiment. The length of the source gas supply pipe 73 is preferably formed such that the distance L3 from the ejection port 77x to the outer surface of the plastic container 11 is 5 ~ 30 mm. At a distance of 5 ~ 30 mm, it is possible to form a uniform thin film on the outer surface of the plastic container 11. If the distance is greater than 30 mm, it is difficult to form a thin film on the outer surface of the plastic container 11, and if the distance is less than 5 mm, it becomes difficult to discharge the source gas.

As another embodiment of the positional relationship of the thermal catalyst 18 and the source gas supply pipe 73, the thermal catalyst or of being placed inside the source gas supply pipe in the same manner as in the case of Figure 10 , for example. At this time, if the inner diameter of the source gas supply pipe is greater than 10 mm, for example, the uniformity of the film distribution will improve. By causing the source gas to contact the thermal catalyst within the source gas supply pipe, it is possible to discharge the chemical species from the source gas supply pipe. Because the thermal catalyst is configured to the interior of the source gas supply pipe, the distance between the thermal catalyst and the surface of the plastic container may be greater, and this makes it possible to control the generation of the thermal deformations of the plastic container. In order to avoid thermal deformation of the plastic container 11, the cooling means 29 such as a cooling pipe through which water or the like flows is preferably provided to the interior or exterior of the vacuum chamber 60 so as to to prevent the lower chamber 63 from increasing its temperature. A heating energy supply 20 is connected to the thermal catalyst 18 through the connector portions 79a, 79b and the wiring 19. By applying electricity to the thermal catalyst 18 with the heating energy supply 20, the thermal catalyst 18 generates heat. In the present embodiment, the maximum temperature at the time the thermal catalyst 18 is heated is preferably less than the temperature at which the thermal catalyst softens. Further, when the thermal catalyst 18 is tungsten, the operating temperature of the thermal catalyst is preferably 1600 ~ 2100 ° C. In addition, a discharge pipe 22 communicates with the space inside the upper chamber 65 through a vacuum valve 8, and the air from the reaction chamber 12 inside the vacuum chamber is discharged by a vacuum pump. discharge not shown in the drawings. Also in the second embodiment, with another embodiment thereof, in order to control the reactions between the thermal catalyst and the source gas below 1590 ° C, a triple pipe structure like the supply gas supply pipe 23 in Fig. 2 of the first embodiment can be used for the source gas supply pipe 73, and a housing mechanism of which houses the thermal catalyst 18 can be provided within the source gas supply pipe 73. In this case, Because the thermal catalyst 18 is placed only in the outlet portion of the gas ejection port 77x of the source gas supply pipe 73, a plurality of point-type technical catalysts are placed on the periphery of the plastic container 11. In the second mode, the source gas species and the resin type of the plastic container are the same as in the case of the first mode. In the manufacturing apparatus of both the first embodiment and the second embodiment, because the thermal catalyst can decompose the source gas only by passing an electric current, it is possible to form a thin gas barrier film on a large number of plastic containers. at the same time if a plurality of thermal catalysts is prepared. Figure 6 is a conceptual drawing of an apparatus for forming a thin gas barrier film simultaneously on the inner surface of a plurality of plastic containers. In Figure 6, a large number of plastic containers 11 are placed and aligned to the interior of a lower chamber 13, a thermal catalyst 18 and a source gas supply pipe 23 as those of Figure 1 are inserted into the nozzle portion of each plastic container 11, and a thin film of gas barrier is formed. In addition, Figure 7 is a conceptual drawing of an apparatus for forming a thin gas barrier film simultaneously on the outer surface of a plurality of plastic containers 11. In Figure 7, a large number of plastic containers 11 are placed and align to the interior of a lower chamber 63, a thermal catalyst 18 is placed respectively around the periphery of each plastic container 11, and after the source gas coming from the source gas supply pipe 73 makes contact with the thermal catalyst 18 , the plastic container 11 is discharged. Here, the nozzle portion is fixed by the rotating bottle mechanism 32, and a thin film is formed on the outer surface while the plastic container 11 is rotating. Also, Figure 8 is a conceptual drawing of an apparatus for forming a thin gas barrier film simultaneously on the outer surface of a plurality of plastic containers sticos 11 online. In Figure 8, the plastic containers are moved by a conveyor to a bottle alignment chamber 40, a discharge chamber 41, a thin film forming chamber 42, a vacuum release chamber 43 and an extraction chamber 44 , in that order. In the thin film forming chamber 42, the thermal catalyst 18 is placed along the side wall of the chamber. In the thin film forming chamber 42, the source gas is discharged to the thermal catalyst 18, the interior of the chamber is filled with the chemical species formed by the decomposition of the source gas, and the formation of the film is performed when the plastic containers 11 pass through the thin film forming chamber 42. In the manufacturing apparatus of both the first and second modes, it is possible to use the same vacuum chamber even when the shapes of the containers are different, there is no the need for a high frequency energy supply, and the film formation can be carried out in a plurality of containers inside a vacuum chamber. In this way, the apparatus becomes cheaper than film forming apparatuses that use a high frequency energy source. In the manufacturing apparatus of both the first embodiment and the second embodiment, given the fact that the plastic container 11 will easily undergo thermal deformation because the source gas 33 becomes a hot gas, preferably the cooling medium is provided. container. Figure 11 is a conceptual drawing for describing the container cooling medium, where (a) is the case where the formation of film on the inner surface of the plastic container is carried out, and (b) it is the case where the formation of film is carried out on the outer surface of the plastic container. As shown in Figure 11 (a), the apparatus for manufacturing the first mode in which the source gas 33, which is a hot gas, is discharged into the plastic container 11 preferably has a container cooling means 51. which applies a cooled liquid or gas 50 to the outer surface of the plastic containers 11. The container cooling medium 51 is a water tank in which the plastic containers 11 are immersed in a liquid such as water or the like, and a shower in the case where the plastic containers 11 are rinsed with a liquid such as water or the like. In addition, it is a watering can in the case where a gas such as cooled nitrogen gas or cooled carbon dioxide gas or the like is discharged into the plastic containers 11. The cooled nitrogen gas and the cooled carbon dioxide gas can be easily obtained using liquid nitrogen and dry ice, respectively. As shown in Fig. 11 (b), the apparatus for manufacturing the second mode in which the source gas 33, which is a hot gas, is discharged to the outer surface of the plastic container 11 preferably has the container cooling means 51 which applies the cooled liquid or gas 50 to the inner surface of the plastic containers 11. The cooling medium of vessel 51 is a liquid filling device in the case where the plastic containers 11 are filled with a liquid such as water or the like, and is a bellows in the case where a gas such as nitrogen gas cooled home carbon dioxide cooled to the like is discharged onto the inner surface of the plastic containers 11. Another embodiment of the thin film forming chamber 42 of Figure 8 is shown in Figure 12. The source gas supply pipes 23 and the cooling medium of containers 51 are alternately configured on the side wall of the thin film forming chamber 42 along the direction of movement of the receivers. plastic pins 11. The plastic containers 11 move along a conveyor (the drawings are not shown), and are made to rotate. Here, the source gas supply pipe 23 uses the type shown in Figure 10. The container cooling medium 51 uses the type that discharges cooled nitrogen gas. When the plastic containers 11 move while being rotated by the conveyor, the source gas activated by the thermal catalyst is discharged from the source gas supply line 23, and then the cooled nitrogen gas is discharged by the container cooling medium 51. , and these are carried out alternately. At this time, the formation of a thin film progresses. Next, with reference to Figure 1, a method will be described for the case where a thin film of hydrogen-containing SiNx is formed as a thin gas barrier film on the inner surface of the plastic container 11 using the apparatus 100 for manufacturing an elastic gas barrier vessel. The plastic container 11 is a 500 ml round PET bottle. The thickness of the container wall is approximately 0.3 mm. The method for manufacturing a gas barrier plastic container according to the first embodiment is a manufacturing method in which a thin gas barrier film is formed while the source gas 33 is discharged into the plastic container 11. In particular, the The method for manufacturing a plastic gas barrier vessel according to the first embodiment has a process in which the inside of the vacuum chamber 6 is discharged which houses the plastic container 11 in order to form a set pressure, and a process in which while maintaining in the state of supply of electricity to the thermal catalyst 18 placed inside the vacuum chamber 6 to generate heat above a preset temperature, the source gas 33 is discharged into the thermal catalyst 18 to decompose the source gas 33 and create the chemical species 34, so that a thin film of gas barrier is formed by the chemical species 34 that reaches the surface interior of the plastic container 11. Firstly, the vent (the drawings are not shown) opens to open the interior of the vacuum chamber 6 to the atmosphere. In a state where the upper chamber 15 is withdrawn, the plastic container 11 is inserted from the upper opening of the lower chamber 13 and is housed in the reaction chamber 12. Then, the placed upper chamber 15 descends, and the supply line of source gas 23 and the thermal catalyst 18 fixed thereto provided in the upper chamber 15 are inserted into the plastic container 11 from the nozzle portion 21 of the plastic container. Then, by connecting the upper chamber 15 to the lower chamber 13 by means of the O-type seal 14, the reaction chamber 12 forms a sealed space. At this time, the gap between the inner wall surface of the lower chamber 13 and the outer wall surface of the plastic container 11 remains approximately uniform, and the gap between the inner wall surface of the plastic container 11 and the thermal catalyst 18 is also kept approximately uniform. Next, after closing the vent (not shown in the drawings), the air inside the reaction chamber 12 is discharged when operating the discharge pump (not shown in the drawings) and opening the valve to vacuum 8 At this time, not only the space inside the plastic container 11, but also the space between the outer wall surface of the plastic container 11 and the inner wall surface of the lower chamber 13 are discharged to form a vacuum. Particularly, the entire reaction chamber 12 is discharged. Then, the interior of the reaction chamber 12 undergoes a pressure reduction until a required pressure is reached, for example, 1 ~ 100 Pa. In this respect, if the pressure is less than 1 Pa, the discharge will take a long time, and the cost of thin film formation will increase. Furthermore, if a pressure greater than 100 Pa is preferred, there will be many impurities inside the plastic containers 11, and it will not be possible to obtain a container having good barrier properties. Then, the electricity is supplied to the thermal catalyst 18 to generate heat at a pre-set temperature, for example, 1700 ° C. Next, a source gas 33 such as ammonia (NH3), silane (SiH4), hydrogen (H2) and the like to the source gas supply pipe 23 from the gas flow controllers 24a ~ 24c, and the gas are supplied. source 33 is discharged to the thermal catalyst 18 heated to 1700 ° C from the gas ejection port 17x to the interior of the plastic container 11 which experienced a reduction in pressure at a preset pressure. The supply rate of the source gas is 100 cc / min for ammonia, 3 cc / min for silane and 50 cc / min for hydrogen gas, for example, and the pressure inside the plastic container 11 is adjusted to 10 ~ 30 Pa After completion of the temperature increase of the thermal catalyst 18 exceeds 1600 ° C, it preferably initiates the discharge of the source gas. From the beginning of the formation of the film, it is possible to create a chemical species sufficiently activated by the thermal catalyst 18, and it facilitates obtaining a film having good gas barrier properties. When the source gas 33 contacts the thermal catalyst 18, specific chemical species 34 are created. A pre-established thin film is discarded by this chemical species 34 which reaches the inner wall of the plastic container 11. The reaction of mono-silane in the The surface of the thermal catalyst 18 and the periphery thereof is shown by Equation 1 and Equation 2. (Eq. 1) SiH 4? Yes * + 4H * (EC.2) YES4 + H *? SiH3 * + H2 It is considered that SiH3 * is the main species of precipitation. In addition, the main ammonia reaction is demonstrated by Equation 3. (Eq. 3) NH3? NH2 * + H * NH2 * is considered the main species of precipitation. In addition, the main hydrogen reaction is shown in Equation 4. (Eq. 4) H2? 2H * H * is considered to be used primarily to assist the gas phase reactions and the surface reactions of the material receiving the precipitation. H * is generated even without using hydrogen as a material gas, but by flowing hydrogen gas as a material gas into the reaction chamber 12, it is possible to generate H * in large quantities, and this exhibits an effect on the acceleration of reactions. In addition, SiH3 * and NH3 * undergo reactions basically according to the thermal energy of the material receiving the precipitation, the thermal energy of the deposition species, and the presence of auxiliary components to the reaction such as H * and the like on the surface of the material that receives the precipitation, and it is supposed to form a silicon hydride film as shown in Equation 5. In addition, in the description provided earlier, the symbol * indicates a radical state.

(Eq. 5) YESH3 * + NH2? SiNx In the present manufacturing method, in the chemical reaction shown by Equation 5, hydrogen at a pre-established atomic concentration is collected by SiNx, and a thin film of SiNx with hydrogen content is formed. In the catalytic chemical vapor waste method, the adhesion between the plastic container 11 and the gas barrier thin film is very good. When the hydrogen gas is introduced from the source gas channel 17, the hydrogen gas is activated by a catalytic decomposition reaction with the thermal catalyst 18, and cleaning can be performed using this specificity in order to extract the natural oxidation film from the surface of the plastic container 11. Particularly, the activated hydrogen H * reacts with O (oxygen) on the surface of the plastic container 11, and pulls the O (oxygen) . In addition, the O (oxygen) and H * react to form H20, and the cleaning is performed by discharging it from the reaction chamber 12 via the discharge pipe 22. When the NH3 gas is introduced from the source gas channel 17 , a surface process is carried out in which the surface of the plastic container 11 is reformed and stabilized by the activated species created by a catalytic decomposition reaction with the thermal catalyst 18. Particularly, when the activated NH2 * reaches the surface of the plastic container in the same way, reactions with O (oxygen) are generated from the surface of the plastic container 11, and cleaning is carried out. When the thin film reaches a preset thickness, the source gas supply 33 is stopped, and then the interior of the reaction chamber 12 is discharged again, and the reaction chamber 12 is set at atmospheric pressure. Then, the upper chamber 15 is opened, and the plastic container 11 is withdrawn. The film thickness of the thin film depends on the type of thermal catalyst 18, the pressure of the source gas inside the plastic container 11, the flow rate of the source gas, the amount of time that the source gas is discharged to the thermal catalyst 18, the type of source gas and the like, but it is understood that 5-100 nm is preferred in order to optimize the compatibility of the absorption control effect of the source gas. Low organic components and the effect of improving the gas barrier properties, adhesion with the plastic container, durability and transparency and the like. Furthermore, it is understood that the hydrogen content value of the SiNx thin film with hydrogen content obtained as measured by RBS (Rutherford Backscattering Spectrometry) preferably has a hydrogen content ratio of 1-10 atomic% . At this time, the oxygen permeability of the vessel was measured, and the oxygen permeability was 0.0010 cc / vessel / day. In addition, the evaluation method is explained below. Oxygen permeability The oxygen permeability of this vessel was measured under the conditions of 23 ° C and an RH (room humidity - ambient humidity) of 90% using an Oxtran 2/20 manufactured by Modern Control Company, and the value of the measurement after 20 hours from the start of the replacement of the nitrogen gas. Film Thickness The thickness of the DLC film was measured using a DEKTAK3 manufactured by the Veeco Company. It is understood that if the film thickness of the SiNx thin film with hydrogen content is less than 5 nm, the oxygen permeability will become high and the gas barrier properties will decrease, and if it exceeds 100 nm, it will be easy for cracks are generated in the film. Furthermore, it is understood that if the ratio of hydrogen content of the thin SiNx film to a hydrogen content is less than 1 atomic%, the film will harden and easily form cracks, and become brittle. It is understood that if the ratio of hydrogen content exceeds 10 atomic%, the oxygen permeability will become high and the gas barrier properties will decrease. From these facts, in the plastic container of which it has gas barrier properties, a thin film of SiNx with hydrogen content is formed as a thin gas barrier film on the surface of the plastic container, and the thin film of SiNx with hydrogen content has a film thickness of 5 ~ 100 nm, and preferably 10 ~ 50 nm, and a hydrogen content ratio of 1 ~ 10 atomic%, and preferably 3-6% atomic. In addition, this plastic container having gas barrier properties can completely control the absorption of low organic compounds such as odor components and the like, can be used as a container container for wider applications, and can be used as a returnable container. Furthermore, in the case where the thin film is formed on the inner surface of the plastic container, there is no risk that the thin film formed will be damaged during handling of the plastic container. In addition, when forming a thin film, there is no loss of transparency for the plastic container.

Next, with reference to Figure 3, a method will be written for the case where a thin film of hydrogen-containing SiNx is formed as a thin gas barrier film on the outer surface of the plastic container 11 using the apparatus 300 to manufacture a plastic gas barrier vessel. The plastic container 11 is a 500 ml round PET bottle. The thickness of the container wall is approximately 0.3 ml. The method for manufacturing a gas barrier plastic container according to the second embodiment is a manufacturing method in which a thin gas barrier film is formed while the source gas 33 is discharged into the plastic container 11. In particular, the The method for manufacturing a gas barrier plastic container according to the second embodiment has a process in which the interior of the vacuum chamber 60 housing the plastic container 11 is discharged to form a pre-set pressure, and a process in which while maintaining a state of electricity supply to the thermal catalyst 18 is placed inside the vacuum chamber 60 to generate heat above a pre-set temperature, the source gas 33 is discharged into the thermal catalyst 18 to decompose the source gas 33 and create the chemical species 34, whereby a thin film of gas barrier is formed by the chemical species 34 that reaches the surface outside of the plastic container 11. Firstly, the defile (the drawings are not shown) is opened in order to open the interior of the vacuum chamber 60 towards the atmosphere. In a state where the upper chamber 65 is removed, the nozzle portion of the plastic container 11 will be initiated in the bottle citation mechanism 32 in the reaction chamber 12. Then, the placed upper chamber 65 descends towards the lower chamber 63, and the gas ejection port 77x of the source gas supply pipe 73 provided in the lower chamber 63 is facing the outer surface of the plastic container 11. At the same time, the thermal catalyst 18 is placed on the periphery of the plastic container 11. Then, by connecting the upper chamber 65 to the lower chamber 63 through the O-type seal 14, the reaction chamber two forms a sealed space. At this time, the gap between the inner wall surface of the lower chamber 63 and the outer wall surface of the plastic container 11 remains approximately uniform, and the gap between the outer wall surface of the plastic container 11 and the thermal catalyst 18 it also remains approximately uniform. Then, after closing the gorge (the drawings are not shown), the air inside the reaction chamber 12 is discharged when operating the discharge pump (the drawings are not shown) and opening the valve to vacuum 8. In at this time, both the space inside and the space outside of the plastic container 11 are discharged to form a vacuum. Particularly, the entire reaction chamber 12 is discharged. Then, the interior of the reaction chamber 12 undergoes a pressure reduction until the required pressure is reached, for example, 1-100 Pa. The reason for forming this pressure range it is the same as the reason explained in the method of manufacturing a plastic gas barrier vessel according to the first embodiment. Then, the thermal catalyst 18 is supplied with electricity to generate heat at a pre-set temperature of 1700 ° C, for example. Next, a source gas 33 such as ammonia (NH3), silane is supplied.

(SiH4), hydrogen (H2) and the like to the source gas supply pipe 73 from the gas flow controllers 24a-24c, and the source gas 33 is discharged to the thermal catalyst 18 heated to 1700 ° C from the 77x gas ejection hole inside the plastic container 11 which experienced a pressure reduction at a preset pressure. The supply rate of the source gas is the same as the case described in the method for manufacturing a plastic gas barrier vessel according to the first embodiment. The pressure inside the reaction chamber 12 is adjusted to 10-30 Pa for this source gas. After the temperature increase of the thermal catalyst 18 above 1600 ° C completed in this way, preferably began the discharge of the source gas. In the same manner as in the case described in the method for manufacturing a plastic gas barrier vessel according to the first embodiment, when the source gas 33 makes contact with the thermal catalyst 18, the specific chemical species 34 are created, and a thin film of hydrogen-containing SiNx is formed on the outer surface of the plastic container 11. Here too, the adhesion between the plastic container 11 and the gas barrier thin film is very good. When the thin film reaches a preset thickness, supply of the source gas 33 is stopped, and then the interior of the reaction chamber 12 is discharged again, a gas leak is introduced not shown in the drawings, and the reaction chamber 12 It is established at atmospheric pressure. Then, the upper chamber 65 is opened, and the plastic container 11 is removed. Here, it is understood that the film thickness formed is preferably 5 ~ 100 nm. Further, it is understood that the hydrogen content value of the SiNx thin film with hydrogen content obtained as measured by RBS (Rutherford Backscattering Spectrometry) preferably has a hydrogen content ratio of 1-10 atomic% . At this time, the oxygen permeability of the vessel was measured, and the oxygen permeability was 0.0010 cc / vessel / day. Particularly, in the plastic container having gas barrier properties obtained by the method of manufacturing the second embodiment, a thin film of SiNx containing hydrogen is formed as a thin gas barrier film on the outer surface of the plastic container , and the SiNx thin film with hydrogen content has a film thickness of 5-100 nm and a hydrogen content ratio of 1-10 atomic%. Then, with reference to Figure 2, a description is given for the method of manufacturing a plastic gas barrier vessel according to the third embodiment in which a thin film of hydrogen-containing SiNx is formed when charging the chamber of reaction 12 with the source gas using the apparatus 200 to manufacture a plastic gas barrier vessel. Particularly, the method for manufacturing a plastic gas barrier vessel according to the third embodiment has a process in which after at least the space inside the plastic container 11 housed in the reaction chamber 12 is filled with the gas source 33 under a preset pressure, the supply of the source gas 33 stops in order to stop the inward and outward flow of gas into the reaction chamber 12, and a process in which while maintaining a state of electricity supply to the thermal catalyst 18 to generate heat above a pre-set temperature, the thermal catalyst 18 is guided into the space filled with the source gas 33 in order to decompose the source gas 33 and create the chemical species 34, whereby a film is formed Delegate gas barrier by the chemical species 34 that reaches the inner surface of the plastic container 11. Also, in Figure 12, the method of manufacturing the case The gas source supply pipe of Figure 10 is used where Figure 12 is shown, but this method of manufacture is another embodiment of the method for manufacturing a plastic gas barrier vessel according to the second embodiment. First, the vent (do not show the drawings) opens to open the interior of the vacuum chamber 6 towards the atmosphere. In a state where the upper chamber 15 is withdrawn, the plastic container 11 is inserted from the upper opening of the lower chamber of 13 and is housed in the reaction chamber 12. Then, the upper placed chamber 15 descends, and the tubing supply of source gas 23 and the thermal catalyst 18 housed therein provided to the upper chamber 15 are inserted into the plastic container 11 from the nozzle portion 21 of the plastic container. Then, by connecting the upper chamber 15 with the lower chamber 13 through the type 0 14 gasket, the reaction chamber 12 forms a sealed space. At this time, the gap between the inner wall surface of the lower chamber 13 and the outer wall surface of the plastic container 11 remains approximately uniform, and the gap between the inner wall surface of the plastic container 11 and the thermal catalyst 18 it also remains approximately uniform. Then, after closing the vent (the drawings are not shown), the air inside the reaction chamber 12 is discharged when operating the discharge pump (not shown in the drawings) and opening the vacuum valve 8. In this At this time, not only the space inside the plastic container 11, but also the space between the outer wall surface of the plastic container 11 and the inner wall surface of the lower chamber 13 are discharged to form a vacuum. Then, the interior of the reaction chamber 12 undergoes a pressure reduction until it reaches, for example, a required pressure of 1-5 Pa. Then, electricity is supplied to the thermal catalyst 18 to generate heat at a pre-set temperature, for example , from 1600 - 2000 ° C. Then, a main valve not shown in the drawings is closed and a fixed amount of the source gas 33 is discharged from the source gas supply pipe 23. At this time, the source gas 33, NH3 (represented by the symbol 33a) passes. through the source gas channel 17a of the interior pipe of the triple pipe and discharged from the tip thereof, and the SiH4 and the H2 (both represented by the symbol 33b) are discharged from the source gas channel 17b of the exterior pipe of the triple pipe. In this way, the inside of the plastic container is filled with a pre-set amount of the source gas 33. Then, the valves 25e and 25f are closed. Furthermore, the valve 8 is closed. In this way, at least the space inside the plastic container 11 housed in the reaction chamber 12 is filled with the source gas 33 under a preset pressure, and the flow stops in and towards outside the gas in the reaction chamber 12. Then, the thermal catalyst 18 placed inside the source gas channel 17a is inserted into the reaction chamber 12 by extending the inner pipe 36 made of an insulating ceramic equipped with the telescopic mechanism. At that time, the silane gas which is the full source gas in the reaction chamber 12 is decomposed, and a delegated SiNx film with hydrogen content is formed on the inner surface of the container by the reaction process described above. The formation of the thin film is completed as soon as all the bridge gas 33 is decomposed. Because the thickness of the thin film formed is determined by the amount of purged source gas 33 in the reaction chamber 12, it is easier to control the thickness of the thin film formed. In the case of a thin film of hydrogen-containing SiNx, the required amount of source gas 33 sealed in a 500 ml bottle is 0.9 - 18.5 ce for SiH4, and the proportion of SiH4 and the other source gases is SiH4: NH3: H2 = 1: 16.7: 33.3. In the method for manufacturing a plastic gas barrier vessel according to the third embodiment, a thin film of hydrogen-containing SiNx is formed as a thin gas barrier film on the inner surface of the plastic container in the same manner as in the method of manufacturing the first embodiment, whereby a container is obtained in which the SiNx thin film with hydrogen content and a film thickness of 5-100 nm and a hydrogen content ratio of 1 ~ 10 atomic% In addition, there is one embodiment of a manufacturing method in which the source gas supply line 73 of the apparatus 300 for manufacturing a plastic gas barrier vessel of Figure 3 assumes the same structure as the source gas supply line 23. of Figure 2. Particularly, in the apparatus 300 for manufacturing a source gas supply pipe of Figure 3, if a housing mechanism for housing the thermal catalyst 18 is provided inside the source gas supply pipe (the type of Figure 2) , it is possible to form a thin film of SiNx with hydrogen content on the outer surface of the container when filling the reaction chamber 12 with the source gas 33. Particularly, the method for manufacturing a plastic gas barrier vessel according to the fourth This method has a process in which after at least the space outside of the plastic container 11 housed in the reaction chamber 12 is filled with the source gas 33 under a preset pressure, the supply of source gas 33 is stopped in order to stopping the flow in and out of the gas in the reaction chamber 12, and a process in which while maintaining a state of supply of electricity to the catalyst tea In order to generate heat above a pre-set temperature, the thermal catalyst 18 is guided into the space filled with the source gas 33 in order to decompose the source gas 33 and create the chemical species 34, whereby a thin film is formed gas barrier by the chemical species 34 that reaches the outer surface of the plastic container 11. After that, a description will be given which assumes a manufacturing apparatus in which the source gas supply pipe 73 in the apparatus 300 for manufacturing a gas barrier of Figure 3, the plastic container is replaced with the source gas supply line 23 of Figure 2. First, the vent is opened (not shown in the drawings) in order to open the interior of the vacuum chamber 60 to the atmosphere. In a state where the upper chamber 65 is withdrawn, the nozzle portion of the plastic container 11 is inserted into the rotating bottle mechanism 32 in the reaction chamber 12. Then, the upper chamber positioned 65 descends towards the lower chamber 63, and the source gas supply pipe (the type of Figure 2) and the thermal catalyst 18 fixed thereto provided in the lower chamber 63 are placed on the periphery of the plastic container 11. Then, by connecting the upper chamber 65 to the lower chamber 63 through the O-type seal 14, the reaction chamber 12 forms a sealed space. At that time, the gap between the inner wall surface of the lower chamber 63 and the outer wall surface of the plastic container 11 remains approximately uniform, and the gap between the outer wall surface of the plastic container 11 and the thermal catalyst 18 it also remains approximately uniform. Then, after closing the vent (not shown in the drawings), the air inside the reaction chamber 12 is discharged when operating the discharge pump (not shown in the drawings) and opening the vacuum valve 8. In at this time, not only the space outside of the plastic container 11, but also the space between the outer wall surface of the plastic container 11 and the interior wall surface of the lower chamber 63 is discharged to form a vacuum. Then, the interior of the reaction chamber 12 undergoes a reduction in pressure until a required pressure is reached, for example, from 1-5 Pa. Then, electricity is supplied to the thermal catalyst 18 to generate heat at a pre-set temperature, for example, 1600-2000 ° C. Next, a main valve not shown in the drawings is closed and a fixed amount of the source gas 33 is discharged from the source gas supply line (the type of Figure 2). At this time, the source gas 33, NH3, passes through the source gas channel of the interior pipe of the triple pipe and discharges from the tip of the same, and the SiH4 and H2 are discharged from the gas channel source of the exterior pipe of the triple pipe. In this way, the interior of the plastic container 11 is filled with a pre-set amount of the source gas 33. Then, the valve 25d is closed. In this way, at least the space to the outside of the plastic container 11 housed in the reaction chamber 12 is filled with the source gas 33 under a preset pressure, and the flow into and out of the gas in the reaction chamber is stopped. 12. Then, the thermal catalyst 18 placed inside the source gas channel 17a is inserted into the reaction chamber 12 by extending the inner pipe (symbol type 36 of Figure 2) made of an insulating ceramic equipped with the telescopic mechanism . At this time, the silane gas which is the source gas filling the interior of the reaction chamber 12 is decomposed, and a thin film of SiNx with hydrogen content formed on the outer surface of the plastic container 11 is formed by the process of reaction described previously. The formation of the thin film is completed as soon as all the source gas 33 is decomposed. In the method of manufacturing a plastic gas barrier vessel according to the fourth embodiment, a delegated film of SiNx with hydrogen content is formed as a thin film of gas barrier on the outer surface of the plastic container in the same way as the method of manufacturing the second embodiment, whereby a container is obtained in which the thin film of SiNx containing hydrogen has a film thickness of 5 - 100 nm and a hydrogen content ratio of 1 ~ and 10 atomic%. In the present invention, it is also possible to form a thin film of SiNx with hydrogen content by the same method in a square 500 ml PET bottle. In addition, by changing the source gas, it is possible to form a thin film of DLC containing hydrogen, a thin film of SiOx containing hydrogen or a thin film of SiCxNy with hydrogen content by the same method. In the embodiments, descriptions were provided in which the gas barrier thin film is formed in some of the outer surface or the inner surface of the plastic container, but these can be combined, and a thin film of gas barrier can be formed on the outer surface and the inner surface of the plastic container. The gas barrier plastic container according to the present invention is a plastic beverage container that has oxygen gas and carbon dioxide gas barrier properties of which is suitable for alcoholic beverages such as beer and the like or soft drinks and the similar.

Claims

NOVELTY OF THE INVENTION Having described the invention as antecedent, the content of the following claims is claimed as property: CLAIMS 1. An apparatus for manufacturing a gas barrier plastic container, characterized in that it comprises: a vacuum chamber for housing a plastic container; a discharge pump that evacuates the chamber under vacuum; a source gas supply pipe formed from an insulating and heat-resistant material which is placed to be inserted into and removed from the interior of the plastic container in order to supply a source gas to the interior of the plastic container; a thermal catalyst that rests on the source gas supply pipe; and a supply of heating energy that supplies electricity to the thermal catalyst to generate heat. The apparatus for manufacturing a gas barrier plastic container according to claim 1, characterized in that the source gas supply line has a cooling line formed integrally to cool the source gas supply line. The apparatus for manufacturing a gas barrier plastic container according to claim 1 or 2, characterized in that the source gas supply pipe is a ceramic pipe formed from a material in which the aluminum nitride, silicon carbide , silicon nitride or aluminum oxide formal main component, or a metal pipe whose surface is coated with a material in which the aluminum nitride, silicon carbon, silicon nitride or aluminum oxide formal main component. The apparatus for manufacturing a gas barrier plastic container according to claim 1, 2 or 3, characterized in that the source gas supply line has a gas ejection hole in the tip of the pipe, and the distance from the Gas ejection hole to the bottom of the plastic container has a length of 5 - 30 mm. The apparatus for manufacturing a gas barrier plastic container according to claim 1, 2, 3 or 4, characterized in that the thermal catalyst is positioned such that the upper end thereof is placed 10-30 mm below the end bottom of the nozzle portion of the plastic container. 6. The apparatus for manufacturing a gas barrier plastic container according to claim 1, 2, 3, 4, or 5, characterized in that the inner surface of the vacuum chamber is black or the inner surface has a surface hardness (Rmax ) of 0.5 μm or more, and the cooling medium is provided inside or outside the chamber. The apparatus for manufacturing a gas barrier plastic container according to claim 1, 2, 3, 4, 5 or 6, further characterized in that it comprises the container cooling means which applies a cooled liquid or gas to the outer surface of the container. plastic container 8. An apparatus for manufacturing a gas barrier plastic container, characterized in that it comprises: a vacuum chamber for housing a plastic container; a discharge pump that evacuates the chamber under vacuum; a thermal catalyst placed on the periphery of the plastic container; a source gas supply pipe that supplies a source gas in the space outside the plastic container to the interior of the vacuum chamber; and a supply of heating energy that supplies electricity to the thermal catalyst to generate heat. The apparatus for manufacturing a gas barrier plastic container according to claim 8, characterized in that the thermal catalyst is plurally placed in rotationally symmetrical positions with respect to the main axis of the plastic container, or is placed to wind spirally with the main axis of the plastic container at the center, or is positioned to wind respectively in parallel in a plurality of cross-sections of the main axis of the plastic container. 10. The apparatus for manufacturing a gas barrier plastic container according to claim 8 or 9, characterized in that the technical catalysts are placed reciprocally at a distance of 5 cm or more. The apparatus for manufacturing a gas barrier plastic container according to claim 8, 9 or 10, characterized in that the thermal catalyst is positioned in such a way that the distance to the outer surface of the plastic container is fixed. The apparatus for manufacturing a gas barrier plastic container according to claim 8, 9, 10 or 11, further characterized in that it comprises the container cooling means which applies a cooled liquid or gas to the inner surface of the plastic container. 13. The apparatus for manufacturing a gas barrier plastic container according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, characterized in that the thermal catalyst is placed at least in the part outlet of the gas ejection hole of the source gas supply pipe. The apparatus for manufacturing a gas barrier plastic container according to claim 13, characterized in that the source gas supply pipe is provided with a housing mechanism for housing the thermal catalyst therein. 15. The apparatus for manufacturing a gas barrier plastic container according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, characterized in that the thermal catalyst is placed inside the the source gas supply pipe. 16. The apparatus for manufacturing a gas barrier plastic container according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, characterized in that the catalyst The thermal part has a portion in which a wire is processed to assume a helical spring shape, a wavy line shape or a zigzag line shape. 17. The apparatus for manufacturing a gas barrier plastic container according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, characterized in that The thermal catalyst is placed along the ejection direction of the source gas. 18. A method for manufacturing a gas barrier plastic container, characterized in that it comprises: a process in which inside a vacuum chamber that houses a plastic container is discharged to form a pre-established pressure; and a process in which while maintaining a state of electricity supply to a thermal catalyst placed inside the vacuum chamber to generate heat above a pre-set temperature, a source gas is discharged into the thermal catalyst to decompose the source gas and creating chemical species, whereby a thin film of gas barrier is formed by the chemical species that reaches at least some of the inner surface or outer surface of the plastic container. 19. The method for manufacturing a gas barrier plastic container according to claim 18, characterized in that the discharge of the source gas begins after the temperature increase of the thermal catalyst ends above the preset temperature. 20. A method for manufacturing a gas barrier plastic container, characterized in that it comprises: a process in which after at least one of the interior or exterior spaces of a plastic container housed in a reaction chamber is filled with a gas source under a preset pressure, the supply of source gas is stopped to stop the flow of gas in and out of the reaction chamber; and a process in which while maintaining a state of electricity supply to a thermal catalyst to generate heat above a pre-set temperature, the thermal catalyst is guided into the space filled with source gas in order to decompose the source gas and create the chemical species, whereby a thin film of gas barrier is formed by the chemical species that reaches at least some of the inner surface or outer surface of the plastic container. 21. A plastic gas barrier vessel, characterized in that a delegated film of hydrogen-containing SiNx, a thin film of DLC containing hydrogen, a thin film of SiOx containing hydrogen or a thin film of SiCxNy with hydrogen content as a thin gas barrier film on at least one of the inner surface or the outer surface of a plastic container, and the hydrogen peroxide-containing SiNx film, the thin film of DLC with hydrogen content, the thin film of SiOx with hydrogen content or the thin film of SiCxNy with hydrogen content has a film thickness of 5-100 nm and a hydrogen content ratio of 1-10% atomic. SUMMARY The object of the present invention is to provide an apparatus for manufacturing a gas barrier plastic container which simultaneously satisfies the condition that the same vacuum chamber can be used even when the container shapes are different, the condition that a high frequency energy source, and the condition that film formation can be performed for a plurality of containers within a vacuum chamber in order to decrease the cost of the apparatus. In an apparatus for forming a film on the inner surface of a container, a thermal catalyst is supported on a source gas supply pipe, and the source gas supply pipe is inserted into the container port, followed by the formation of the movie. In an apparatus for forming a film on the outer surface of a container, a thermal catalyst is placed on the periphery of the plastic, and a source gas is discharged through the source gas supply line while the source gas contacts the source gas. thermal catalyst for film formation. The cooling is done to avoid the thermal deformation of the container by the radiated heat coming from the thermal catalyst. For example, a container on which a thin film of SiNx containing hydrogen has a film thickness of 5 to 100 nm and a hydrogen content ratio of 1 to 10 atomic% is obtained.