TW201326449A - Method for producing gas barrier plastic molded body - Google Patents

Abstract

The purpose of the present invention is to provide a method for forming a gas barrier thin film, which is substantially colorless and has gas barrier properties, on the surface of a plastic molded body by a heating element CVD method using only starting material gases that are highly safe. A method for producing a gas barrier plastic molded body according to the present invention is a method for producing a gas barrier plastic molded body (90), wherein a gas barrier thin film (92) is formed on the surface of a plastic molded body (91), comprising the following film formation step, in which the gas barrier thin film (92) is formed on the surface of the plastic molded body by a heating element CVD method using an organic silane compound represented by the general formula (1) as a main starting material gas and using an oxidation gas as an additive gas, while using a heating element that contains tantalum (Ta) as a main constituent element. In formula (1), n represents 2 or 3, and X represents SiH3, H or NH2.

Description

Method for producing gas barrier plastic molded body

The present invention relates to a method of producing a gas barrier plastic molded body.

Previously, a film was formed on the surface of a plastic molded body to impart gas barrier properties. A film having a gas barrier property mainly composed of an inorganic oxide in a surface area of a plastic container by using a plasma chemical vapor deposition method (hereinafter, chemical vapor deposition (Chemical Vapor Deposition) method) There is a method called a gas barrier film (for example, refer to Patent Document 1). However, in the method of forming a thin film by the plasma CVD method, the plasma may cause damage to the surface of the film when the film is formed, and the density of the film is easily damaged, and it is difficult to obtain a gas with high resistance. Further, the plasma CVD method uses a plasma to decompose a raw material gas to ionize it, and collides ions accelerated by an electric field on a surface of a plastic container to form a thin film. Therefore, a high-frequency power source and a high-frequency power matching device are required. The inevitable problem of expensive equipment.

A method in which a raw material gas is brought into contact with a heat generating body which generates heat, and the generated chemical species is deposited as a thin film on a substrate directly or in a gas phase after passing through a reaction process, that is, a heating body CVD method, Cat-CVD method The CVD method (Catalytic Chemical Vapor Deposition) or the hot-wire CVD method (hereinafter referred to as the heating element CVD method in the present specification) can solve the above problem of the plasma CVD method, and is more electric. The film forming apparatus of the slurry CVD method is a simple and low-cost film forming apparatus which forms a dense film having high gas barrier properties, and thus has attracted attention as a next-generation film forming method. However, if hydrazine hydride such as monodecane, dioxane or trioxane is used as the raw material gas Since the body is self-igniting, it costs a safety device, and the cost advantage is weakened with respect to the film forming apparatus of the plasma CVD method. Therefore, the present applicant has proposed a technique of forming a SiOx film or an AlOx film on the wall surface of a plastic container by using a heat-generating CVD method using a material having a high safety such as a non-self-igniting raw material as a material gas (for example, see Patent Document 2). .

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-200043

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-127053

Since the SiOx film is colorless and transparent and has high gas barrier properties, it is widely used as a gas barrier film. However, SiOx films are known to have problems in water resistance. When the SiOx film contains carbon in the film, the adhesion to the plastic substrate is good. However, if the content of carbon is increased, there is a problem of coloring, and the use is limited. Heretofore, it has been hardly studied to form a gas barrier film which is substantially colorless and has gas barrier properties by using a heat generating CVD method using only a material gas having high safety.

An object of the present invention is to provide a material which is substantially colorless and has a gas barrier by using a heating element CVD method on the surface of a plastic molded body and using only a material gas having a higher safety than the case of using decane or trimethylaluminum. The method of gas barrier film.

The method for producing a gas barrier plastic molded body of the present invention is a method for producing a gas barrier plastic molded body in which a gas barrier film is formed on a surface of a plastic formed body, which comprises the following film forming step: on the surface of the plastic molded body In the heating element CVD method, an organic decane compound represented by the formula (Chemical Formula 1) is used as a main material gas, and an oxidizing gas is used as an additive gas, and a heating element containing cerium (Ta) as a main constituent element is used. The above gas barrier film is formed.

(Chemical Formula 1) H ₃ Si-C _n -X In Chemical 1, 1 is 2 or 3, and X is SiH ₃ , H or NH ₂ .

In the method for producing a gas barrier plastic molded article of the present invention, the organodecane compound is preferably vinyl decane. A film excellent in gas barrier properties can be formed safely and efficiently as compared with the case of using decane or trimethylaluminum.

In the method for producing a gas barrier plastic molded article of the present invention, the oxidizing gas preferably contains carbon dioxide. The degree of oxidation of the film can be controlled, and even if the coloring is small, a high gas barrier property can be exhibited. In particular, if carbon dioxide is used, the degree of oxidation of the film is relatively easy to control, and a wide range of so-called process operations can be obtained.

In the method for producing a gas barrier plastic molded article of the present invention, the mixing ratio of the carbon dioxide to the organic decane-based compound is in the form of 6:100 to 260:100.

In the method for producing a gas barrier plastic molded article of the present invention, the oxidizing gas contains oxygen, and a mixing ratio of the oxygen gas to the organic decane compound is 4:100 to 130:100.

In the method for producing a gas barrier plastic molded body of the present invention, the above The plastic formed body is in the form of a film, a sheet or a container.

In the method for producing a gas barrier plastic molded article of the present invention, the heat generating body is in the form of a metal tantalum (Ta), a tantalum-based alloy or tantalum carbide (TaC _x ).

In the method for producing a gas barrier plastic molded article of the present invention, it is preferred to have a regeneration step of supplying a heating element that supplies an oxidizing gas to the environment and heats the heating element after the film forming step. When a plurality of formed bodies are continuously formed under the same conditions, the gas barrier properties of the latter half of the film are suppressed to be lower than those of the first half of the film.

The present invention can provide a method of forming a substantially colorless film having gas barrier properties by using a heat generating body CVD method on the surface of a plastic molded body and using only a material gas having high safety.

Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited by the description. The embodiment can be variously modified as long as the effects of the present invention are achieved.

First, a film forming apparatus which can form a gas barrier film on the surface of a plastic molded body will be described. Fig. 1 is a schematic view showing one form of a film forming apparatus. The film forming apparatus shown in Fig. 1 is formed by forming a film on the inner surface of the container when the plastic molded body is a container.

The film forming apparatus 100 shown in Fig. 1 includes a vacuum chamber 6 that houses a plastic container 11 as a plastic molded body, an exhaust pump (not shown) that evacuates the vacuum chamber 6 into a vacuum, and a raw material gas supply tube. 23, which is insertably disposed inside the plastic container 11 and supplies a material gas to the inside of the plastic container 11 by An insulating and heat-resistant material is formed; the heating element 18 is supported by the material gas supply pipe 23; and the heating power source 20 is energized to heat the heating element 18.

The vacuum chamber 6 is formed therein with a space for accommodating the plastic container 11, which becomes the reaction chamber 12 for forming a film. The vacuum chamber 6 includes a lower chamber 13 and an upper chamber 15, and the upper chamber 15 is detachably attached to the upper portion of the lower chamber 13 and seals the inside of the lower chamber 13 with an O-ring 14. The upper chamber 15 has an upper and lower driving mechanism (not shown), and moves up and down as the plastic container 11 is moved in and out. The internal space of the lower chamber 13 is formed in a manner slightly larger than the outer shape of the plastic container 11 accommodated therein.

The inner side of the vacuum chamber 6, especially the inner side of the lower chamber 13, is for preventing the reflection of light emitted by the heating of the heating element 18, preferably the inner surface 28 is a black inner wall, or the inner surface has a surface roughness. (Rmax) is a bump of 0.5 μm or more. The surface roughness (Rmax) is measured using, for example, a surface roughness measuring instrument (manufactured by Ulvac Techno, DEKTAX3). In order to make the inner surface 28 a black inner wall, there is a plating treatment such as black nickel plating or black chrome plating, a film processing such as RAYDENT (cold plating) or blackening, or a method of applying a black paint for coloring. Further, it is preferable to provide a cooling device 29 such as a cooling pipe for flowing cooling water inside or outside the vacuum chamber 6, thereby preventing the temperature of the lower chamber 13 from rising. In the vacuum chamber 6, particularly, the following chambers 13 are targeted, because the heat generating body 18 is inserted into the plastic container 11 in a state of being accommodated in the internal space of the lower chamber 13. By preventing the reflection of light and the cooling of the vacuum chamber 6, the temperature rise of the plastic container 11 and the thermal deformation accompanying this can be suppressed. Further, if a chamber 30 including a transparent body through which the emitted light generated by the self-energized heating element 18 can pass is formed, for example, a glass cavity Since the chamber is disposed inside the lower chamber 13, the temperature of the glass chamber contacting the plastic container 11 is hard to rise, so that the thermal influence on the plastic container 11 can be further alleviated.

The material gas supply pipe 23 is supported so as to be suspended in the center of the inner top surface of the upper chamber 15 so as to hang downward. The material gas 33 and the additive gas or the carrier gas used as needed flow into the material gas supply pipe 23 via the flow rate adjusters 24a, 24b, and 24c and the valves 25a, 25b, 25c, and 25d. When the material gas 33 is supplied to the material used as the material gas 33 as a liquid, it can be supplied by a foaming method. In other words, the flow rate is controlled by the flow rate regulator 24a, and the foaming gas is supplied from the gas cylinder 42a to the starting material 41a contained in the raw material tank 40a, and the starting material 41a is vaporized and supplied as the material gas 33. The carrier gas system is housed in the gas cylinder 42c, and is supplied while controlling the flow rate by the flow rate adjuster 24c. In the film forming apparatus shown in Fig. 1, when the material used as the material gas is a gas, it may be deformed into a form in which the raw material gas is filled in the gas cylinder 42a without providing the raw material tank 40a. The flow rate regulator 24a controls the flow rate and supplies it.

The material gas supply pipe 23 preferably includes a cooling pipe and is integrally formed. The structure of the material gas supply pipe 23 is, for example, a double pipe structure. In the material gas supply pipe 23, the inner pipe of the double pipe is the material gas flow path 17, and one end thereof is connected to the gas supply port 16 provided in the upper chamber 15, and the other end is a gas discharge hole 17x. Thereby, the raw material gas system is ejected from the gas ejection hole 17x connected to the front end of the material gas flow path 17 of the gas supply port 16. On the other hand, the pipe outside the double pipe is used to cool the raw material gas supply pipe 23 However, the water flow path 27 functions as a cooling pipe. Further, when the heating element 18 is energized and heated, the temperature of the material gas flow path 17 rises. In order to prevent the temperature from rising, cooling water is circulated in the cooling water flow path 27. In other words, at one end of the cooling water flow path 27, cooling water is supplied from a cooling water supply device (not shown) connected to the upper chamber 15, and the cooling water that has been cooled is returned to the cooling water supply device. On the other hand, the other end of the cooling water flow path 27 is sealed in the vicinity of the gas ejection hole 17x, and the cooling water is folded back here. The raw material gas supply pipe 23 is cooled by the cooling water flow path 27. The thermal impact on the plastic container 11 can be reduced by cooling. Therefore, the material of the material gas supply pipe 23 is preferably an insulator and has a large thermal conductivity. For example, it is preferably a ceramic tube formed of a material mainly composed of aluminum nitride, tantalum carbide, tantalum nitride or aluminum oxide, or mainly composed of aluminum nitride, tantalum carbide, tantalum nitride or aluminum oxide. The material is coated with a metal tube on the surface. The heating element can be stably energized, has durability, and can efficiently discharge heat generated by the heating element by heat conduction.

The material gas supply pipe 23 may be provided as follows, as another form not shown. That is, the raw material gas supply pipe is provided as a double pipe, and the outer pipe is used as a material gas flow path to open a hole in the side wall of the outer pipe, and preferably a plurality of holes are opened. On the other hand, the inner tube of the double pipe of the material gas supply pipe is formed of a dense pipe, and the cooling water flows as a cooling water flow path. The heat generating system is routed along the side wall of the raw material gas supply pipe, and the raw material gas provided in the hole in the side wall of the outer pipe contacts the heat generating body along the side wall, whereby the chemical species can be efficiently generated.

If the gas ejection hole 17x is excessively separated from the bottom of the plastic container 11, it is difficult A film is formed inside the plastic container 11. In the present embodiment, the length of the material gas supply pipe 23 is preferably such that the distance L1 from the gas discharge hole 17x to the bottom of the plastic container 11 is 5 to 50 mm. The uniformity of the film thickness is improved. A uniform film can be formed on the inner surface of the plastic container 11 at a distance of 5 to 50 mm. If the distance is larger than 50 mm, there is a case where it is difficult to form a film on the bottom of the plastic container 11. Further, when the distance is less than 5 mm, there is a case where it is difficult to discharge the material gas, or the film thickness distribution is not uniform. This fact can also be grasped theoretically. In the case of a 500 ml container, since the main body diameter of the container is 6.4 cm, the average free path of air at normal temperature is λ = 0.68/Pa [cm], so the molecular flow is pressure <0.106 Pa, and the viscous flow is pressure > 10.6. Pa, the intermediate flow is 0.106 Pa <pressure < 10.6 Pa. When the gas pressure at the time of film formation is 5 to 100 Pa, the gas flow changes from the intermediate flow to the viscous flow, and the distance between the gas ejection hole 17x and the bottom of the plastic container 11 is optimal.

The heating element 18 promotes decomposition of the material gas in the heating element CVD method. Since it is electrically conductive, it can generate heat by itself by energization. The heating element 18 is formed in a wiring shape, and one end of the heating element 18 is connected to the connecting portion 26a, and the connecting portion 26a is provided below the fixed position of the upper chamber 15 of the material gas supply pipe 23 to connect the wiring 19 to the heating element 18. position. Further, the front end portion is supported by the insulating ceramic member 35 provided on the gas ejection hole 17x. Further, returning, the other end of the heating element 18 is connected to the connecting portion 26b. In this manner, since the heating element 18 is supported along the side surface of the material gas supply pipe 23, it is disposed so as to be positioned on the substantially main axis of the internal space of the lower chamber 13. In Fig. 1, a heating element 18 is illustrated for supply with a raw material gas. Although the axis of the tube 23 is arranged parallel to the periphery of the material gas supply pipe 23, the connecting portion 26a may be spirally wound around the side of the material gas supply pipe 23 as a starting point, and may be fixed to the gas. After the insulating ceramics 35 in the vicinity of the hole 17x are supported, they are folded back and returned to the connecting portion 26b. Here, the heating element 18 is fixed to the material gas supply pipe 23 by being hung on the insulating ceramic 35. In the case of the heat generating body 18 in the vicinity of the gas discharge hole 17x of the material gas supply pipe 23, the heat generating body 18 is disposed on the outlet side of the gas discharge hole 17x. Thereby, the material gas ejected from the gas ejection hole 17x is easily brought into contact with the heating element 18, so that the material gas can be efficiently activated. Here, it is preferable that the heating element 18 is disposed slightly away from the side surface of the material gas supply pipe 23. The purpose is to prevent an abrupt temperature rise of the material gas supply pipe 23. Further, the chance of contact with the material gas ejected from the gas ejection hole 17x and the material gas in the reaction chamber 12 can be increased. The outer diameter of the material gas supply pipe 23 including the heat generating body 18 must be smaller than the inner diameter of the mouth portion 21 of the plastic container. The purpose is to insert the material gas supply pipe 23 including the heating element 18 from the mouth portion 21 of the plastic container. Therefore, when the heating element 18 is separated from the surface of the material gas supply pipe 23 to the extent necessary, the material gas supply pipe 23 is easily contacted when being inserted from the mouth portion 21 of the plastic container. The width of the heating element 18 is preferably 10 mm or more and (the inner diameter of the mouth portion -6) mm or less in consideration of the positional deviation when the mouth portion 21 of the plastic container is inserted. For example, the inner diameter of the mouth portion 21 is about 21.7 to 39.8 mm.

The heating element 18 can generate heat by, for example, energization. In the apparatus shown in FIG. 1, the heating power source 20 is connected to the heating element 18 via the connecting portions 26a and 26b and the wiring 19. The heating element 18 is supplied to the heating element 18 by the heating power source 20 heat. Furthermore, the present invention is not limited to the heat generating method of the heat generating body 18. The upper limit temperature at which the heating element 18 generates heat is preferably set to be lower than the softening temperature of the heating element. If it is more than the softening temperature, there is a case where the heating element is deformed and cannot be controlled.

Further, since the stretching ratio of the plastic container 11 at the time of molding from the mouth portion 21 of the plastic container to the shoulder portion of the container is small, if the heat generating body 18 which generates heat at a high temperature is disposed in the vicinity, deformation due to heat is likely to occur. According to the experiment, if the position where the connection portion 26a, 26b, that is, the connection position of the wiring 19 and the heating element 18, is not separated from the lower end of the mouth portion 21 of the plastic container by 10 mm or more, the shoulder portion of the plastic container 11 is thermally deformed. When it exceeds 50 mm, it is difficult to form a film on the shoulder portion of the plastic container 11. Therefore, the heating element 18 is preferably disposed such that its upper end is located 10 to 50 mm below the lower end of the mouth portion 21 of the plastic container. That is, it is preferable to provide such that the distance L2 between the connecting portions 26a and 26b and the lower end of the mouth portion 21 is 10 to 50 mm. It can suppress the thermal deformation of the shoulder of the container.

Further, the exhaust pipe 22 communicates with the internal space of the upper chamber 15 via the vacuum valve 8, and the air in the reaction chamber 12 inside the vacuum chamber 6 is discharged by an exhaust pump (not shown).

The film forming apparatus shown in Fig. 1 does not require a high frequency power source, and the apparatus is relatively inexpensive compared with the film forming apparatus of the plasma CVD method. The apparatus for forming the gas barrier film 92 on the inner surface of the plastic container has been described. However, when the gas barrier film 92 is formed on the outer surface of the plastic container, for example, the film forming apparatus shown in Fig. 4 of Patent Document 2 can be used. Further, in the case where the plastic formed body is a film or a sheet, for example, the reaction chamber 12 can be set to a cylindrical shape and the film or sheet can be placed along the film. The inner wall is fixed, and a gas barrier film 92 is formed on the surface of the film or sheet. Further, a modification may be made in which a winding device including a roll for continuously feeding a film or sheet of a cylindrical shape and a roll for winding a film or sheet of a film is provided in the vacuum chamber 6. Moreover, the film forming apparatus is not limited to the apparatus shown in FIG. 1, and various modifications can be made, for example, as shown in Patent Document 2.

Next, a method of manufacturing the gas barrier plastic molded body of the present embodiment will be described with reference to Fig. 1 . Fig. 2 is a cross-sectional view showing an example of a gas barrier plastic molded body of the embodiment. The method for producing a gas barrier plastic molded article of the present embodiment is a method for producing a gas barrier plastic molded body 90 in which a gas barrier film 92 is formed on the surface of a plastic molded body 91, and includes the following film forming step: a plastic molded body The surface of 91 (the inner surface of the plastic container 11 in Fig. 1) is an organic decane-based compound represented by the general formula (Chemical Formula 1) as a main raw material gas 33 by using a heating element CVD method, and an oxidizing gas is used as an additive gas. Further, a heat-generating body 18 containing tantalum (Ta) as a main constituent element is used to form a gas barrier film 92.

(Chemical Formula 1) H ₃ Si-C _n -X In Chemical 1, 1 is 2 or 3, and X is SiH ₃ , H or NH ₂ .

(Installation of plastic molded body to film forming apparatus)

First, a vent (not shown) is opened to open the vacuum chamber 6 to the atmosphere. In the state where the upper chamber 15 is removed, the plastic container 11 as the plastic molded body 91 is inserted into the reaction chamber 12 from the upper opening portion of the lower chamber 13 and housed therein. Thereafter, the upper chamber 15 is determined by lowering the position, and the material gas supply pipe 23 attached to the upper chamber 15 and the heat generating body 18 fixed thereto are inserted into the plastic container 11 from the mouth portion 21 of the plastic container. Then, the upper chamber 15 is via O The ring 14 abuts against the lower chamber 13, whereby the reaction chamber 12 becomes a closed space. At this time, the interval between the inner wall surface of the lower chamber 13 and the outer wall surface of the plastic container 11 is kept substantially uniform, and the interval between the inner wall surface of the plastic container 11 and the heat generating body 18 is also kept substantially uniform.

Although the plastic molded body 91 is shown in the form of a container in Fig. 1, it is not limited thereto, and includes a form of a film or a sheet. The shape can be appropriately set depending on the purpose and use, and is not particularly limited. The container includes a container that is capped, bolted or sealed, or a container that is used in an open state without using the container. The size of the opening can be appropriately set depending on the content. The plastic container includes a plastic container having a moderate rigidity and a specific wall thickness, and a plastic container formed of a sheet material having no rigidity. The invention is not limited by the method of manufacture of the container. The contents are, for example, beverages such as water, tea drinks, refreshing drinks, carbonated drinks or fruit drinks, liquids, slims, powders or solid foods. Also, the container may be a recyclable container or a disposable container. The film or sheet comprises a strip of strips, a cut piece. The film or sheet may be either extended or unstretched. The present invention is not limited by the method of manufacturing the plastic formed body 91.

The resin constituting the plastic molded body 91 is, for example, polyethylene terephthalate (PET), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene. Resin (PP, Polypropylene), cycloolefin copolymer resin (COC, Cycloolefin Copolymer, cyclic olefin copolymerization), ionic polymer resin, poly-4-methylpentene-1 resin, polymethyl methacrylate resin, Polystyrene resin, ethylene-vinyl alcohol copolymer resin, acrylonitrile resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, polyamidamine Amine resin, polyacetal resin, polycarbonate resin, polyfluorene resin or tetrafluoroethylene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin. One type of these may be used as a single layer or a laminate, but it is preferably a single layer in terms of productivity. Further, the type of the resin is more preferably PET.

The thickness of the plastic molded body 91 can be appropriately set depending on the purpose and use, and is not particularly limited. For example, when the plastic molded body 91 is a container such as a bottle for a drink, the wall thickness of the bottle is preferably 50 to 500 μm, more preferably 100 to 350 μm. Further, in the case of forming a film of a packaging bag, the thickness of the film is preferably from 3 to 300 μm, more preferably from 10 to 100 μm. In the case where the plastic molded body 91 is a substrate of a flat panel display such as an electronic paper or an organic EL (Organic Electro-Luminescence), the thickness of the film is preferably 25 to 200 μm, more preferably 50 to 100 μm. . Further, in the case of forming a sheet for a container, the thickness of the sheet is preferably from 50 to 500 μm, more preferably from 100 to 350 μm. Further, when the plastic molded body 91 is a container, the gas barrier film 92 is provided on either or both of the inner wall surface and the outer wall surface. Further, when the plastic molded body 91 is a film, the gas barrier film 92 is provided on one surface or both surfaces thereof.

(pressure adjustment step)

Then, after the vent (not shown) is closed, an exhaust pump (not shown) is operated, and the vacuum valve 8 is opened to discharge the air in the reaction chamber 12. At this time, not only the internal space of the plastic container 11, but also the space between the outer wall surface of the plastic container 11 and the inner wall surface of the lower chamber 13 is exhausted to become a vacuum. That is, the entire reaction chamber 12 is exhausted. Moreover, it is preferred to have the reaction chamber 12 The necessary pressure is reduced to reach, for example, 1.0 to 100 Pa. More preferably 1.4 to 50 Pa. If it is less than 1.0 Pa, there is a case where exhaust time is consumed. Further, when it exceeds 100 Pa, there is a case where the amount of impurities in the plastic container 11 increases, and it is impossible to provide a high barrier property. When the pressure is reduced from atmospheric pressure to 1.4 to 50 Pa, a moderate vacuum pressure and a moderate residual vapor pressure from the atmosphere, equipment, and container can be obtained, and an oxide film having barrier properties can be easily formed.

(Power on the heating element)

Then, the heating element 18 generates heat, for example, by energization. The heating element 18 contains tantalum (Ta) as a main constituent element, and for example, a form including a metal tantalum, and an alloy of niobium and an alloy of another metal such as tungsten or tantalum which forms an alloy with niobium. In the case of an alloy, it is preferably contained in an amount of 90% by mass or more. More preferably, it is 99% by mass or more, and further preferably 99.9% or more. The heat generation temperature of the heating element 18 is preferably 1600 ° C or higher. More preferably, it is 1700 ° C or more. Further, the upper limit temperature of the heat generation temperature is preferably set to be lower than the softening temperature of the heat generating body. If it is more than the softening temperature, the heating element 18 may be deformed and may not be controlled. The upper limit temperature is preferably 2400 °C. More preferably 2100 ° C.

The heating element 18 is in the form of tantalum carbide (TaC _x ). The carbon atom in the tantalum carbide (TaC _x ) is preferably more than 0% by mass and not more than 6.2% by mass in terms of a mass ratio. More preferably, it is more than 3.2% by mass and is 6.2% by mass or less. At this time, the element concentration of the carbon atom in the tantalum carbide (TaC _x ) is preferably more than 0 at.% (atomic%) and 50 at.% or less. More preferably, it is more than 33 at.% and is 50 at.% or less. Here, the material containing tantalum (Ta) as a main constituent element means that the material of the heat generating body contains 50 at.% or more of germanium atoms in terms of element concentration.

(introduction of raw material gas)

Thereafter, the material flow rate 33 of a specific flow rate is supplied by the gas flow rate adjuster 24a, and the additive gas of a specific flow rate is supplied by the gas flow rate adjuster 24b. Further, the carrier gas is flow-controlled by the gas flow rate adjuster 24c as needed, and the carrier gas is mixed into the source gas 33 near the valve 25d. The carrier gas is an inert gas such as argon gas, helium gas or nitrogen gas. In this manner, the raw material gas 33 and the additive gas system are controlled by the gas flow rate adjusters 24a and 24b, or in a state where the flow rate is controlled by the carrier gas, and the pressure is reduced to a specific pressure in the plastic container 11 from the raw material gas. The gas discharge hole 17x of the supply pipe 23 is discharged to the heat generating body 18 that generates heat. Preferably, after the heating element 18 is heated up in this manner, the raw material gas 33 is discharged. At the initial stage of film formation, the chemical element 34 can be sufficiently activated by the heating element 18, and the adhesion to the plastic molded body can be further improved.

When the substance used as the material gas 33 is a liquid, it can be supplied by a foaming method. The foaming gas system used in the foaming method is an inert gas such as nitrogen, argon or helium, and more preferably nitrogen. In other words, when the flow rate is controlled by the gas flow rate adjuster 24a while the flow rate is controlled by the gas flow rate adjuster 24a, the starting material 41a in the raw material tank 40a is foamed, and the starting material 41a is vaporized and mixed into the bubbles. In this manner, the material gas 33 is supplied in a state of being mixed with the foaming gas.

The material gas 33 is mainly an organic decane compound represented by the formula (Chemical Formula 1). In Yuhua 1, when n=2, the example of the state of C _n is a state in which a bond between CCs is a single bond (C ₂ H ₄ ), a state in which a bond between CCs is a double bond (C ₂ H ₂ ), and between CCs. The three-button aspect (C ₂ ). When n=3, the example of the state of C _n is a single bond type between CCs (C ₃ H ₆ ), a single bond and a double bond between CCs (C ₃ H ₄ ), and a single bond between CCs. And the three-button aspect (C ₃ H ₂ ). Specifically, the organodecane compound represented by the formula (Chemical Formula 1) is, for example, vinyl decane (H ₃ SiC ₂ H ₃ ), dioxane (H ₃ SiC ₂ H ₄ SiH ₃ ), dialkyl acetylene. (H ₃ SiC ₂ SiH ₃ ), 2-aminoethyl decane (H ₃ SiC ₂ H ₄ NH ₂ ). These may be used singly or in combination. Among them, vinyl decane is more preferable in terms of a higher film forming efficiency.

In the present embodiment, when the organodecane-based compound represented by the formula (Chemical Formula 1) is used as the main raw material gas, the mixed gas in which the auxiliary raw material gas is mixed may be supplied as the raw material gas. Here, the main raw material gas system means that the content of the organic decane-based compound represented by the formula (Chemical Formula 1) is 50% by volume or more, more preferably 80% by volume or more, and particularly preferably 90% by volume or more based on the total capacity of the raw material gas. . By using the auxiliary material gas, the raw material cost can be suppressed, and the gas barrier plastic molded body can be obtained more inexpensively. A secondary feed gas system such as acetylene, methane, ethane.

The supply amount of the material gas 33 is not particularly limited, but is preferably 3 to 200 sccm. More preferably 30~500 sccm. In the case of supplying by the foaming method, the flow rate of the foaming gas is preferably from 3 to 80 sccm, more preferably from 10 to 50 sccm.

The added gas contains an oxidizing gas. Oxidation gas systems such as oxygen (O ₂ ), ozone (O ₃ ), water vapor (H ₂ O), carbon dioxide (CO ₂ ). Among them, carbon dioxide is more preferred. In the present invention, as the oxidizing gas, it is preferred to exclude nitrous oxide (nitrous oxide, N ₂ O).

The supply amount of the additive gas varies depending on the type of the oxidizing gas. For example, when the oxidizing gas is carbon dioxide, the mixing ratio of the supply amount of carbon dioxide to the supply amount of the raw material gas 33 is preferably 6:100 to 260: 100. More preferably, the supply amount to the raw material gas is 100, the supply amount of carbon dioxide is 20 to 200 (CO ₂ : raw material gas = 1:5 to 2:1), and the supply amount to the raw material gas is preferably 100. The supply of carbon dioxide is 40 to 100 (CO ₂ : raw material gas = 1:2.5 to 1:1). Further, when the oxidizing gas is oxygen, the mixing ratio of the supply amount of oxygen to the supply amount of the material gas 33 is preferably 4:100 to 130:100. More preferably, the supply amount to the raw material gas is 100, the supply amount of oxygen is 10 to 100 (O ₂ : raw material gas = 1:10 to 1:1), and the supply amount to the raw material gas is preferably 100. The supply of oxygen is 12 to 50 (O ₂ : raw material gas = 1:8.3 to 0.5:1). In the case where the flow rate of the material gas is 50 sccm, the case where the oxidizing gas is carbon dioxide is preferably set to a flow rate of carbon dioxide of 3 sccm or more and 130 sccm or less, and more preferably set to 10 sccm or more and 100 sccm or less are particularly preferably set to 20 sccm or more and 50 sccm or less. Further, when the oxidizing gas is oxygen, the flow rate of oxygen is preferably set to 2 sccm or more and 65 sccm or less, more preferably 5 sccm or more and 50 sccm or less, and particularly preferably set to 6 sccm or more. Below 25 sccm.

The flow rate of the carrier gas is not particularly limited, and is preferably 0 to 80 sccm. More preferably 5~50 sccm. In the present specification, the flow rate of the carrier gas is 0 sccm, and only the source gas 33 and the additive gas are supplied without using the carrier gas. In this case, the gas flow rate adjuster 24c is not used.

(film formation)

When the source gas 33 and the additive gas come into contact with the heating element 18, a chemical species 34 containing Si, C, and O as constituent elements is formed. By making the chemical species 34 The inner wall of the plastic container 11 is reached, and a gas barrier film containing at least bismuth, carbon and oxygen as constituent elements is deposited. In the film formation of the gas barrier film, the time during which the heating element 18 generates heat and the raw material gas 33 and the additive gas are sprayed onto the heating element 18 (hereinafter, referred to as a film formation time) is preferably 0.5 to 10 seconds. More preferably 1.0 to 6.0 seconds. The pressure in the vacuum chamber at the time of film formation is preferably reduced to, for example, 1.0 to 100 Pa, more preferably 1.4 to 50 Pa.

When the heating body CVD method is used, the adhesion between the plastic container 11 and the formed film is extremely excellent. When hydrogen gas is introduced from the material gas channel 17, the hydrogen gas is activated by the contact decomposition reaction with the heating element 18, and the surface of the plastic container 11 can be cleaned by the active species. More specifically, a hydrogen abstraction reaction or an etching action of an activated hydrogen H* or a hydrogen radical (atomic hydrogen) H can be expected, and for example, it can be used to improve the adhesion of a film.

When the NH ₃ gas is introduced from the material gas channel 17 , the surface of the plastic container 11 can be modified and stabilized by using the active species generated by the contact decomposition reaction with the heating element 18 . deal with. More specifically, a crosslinking reaction to the nitrogen-containing functional group of the surface or the polymer chain of the plastic can be expected.

(the end of film formation)

When the film reaches a certain thickness, the supply of the material gas 33 is stopped. Then, after the inside of the reaction chamber 12 is again exhausted, a leak gas (not shown) is introduced to bring the atmospheric pressure into the reaction chamber 12. Thereafter, the upper chamber 15 is opened to take out the plastic container 11. In the method for producing a gas barrier plastic molded article of the present embodiment, it is preferable that the film thickness of the gas barrier film 92 is 5 to 100 nm. More preferably, it is 10 to 85 nm, and particularly preferably 30 to 50 nm. If it is less than 5 nm, it will not be able to play. High resistance to gas. If it exceeds 100 nm, there is a case where transparency is lowered and cracking of the film is likely to occur. Also, it is not economical.

The heating element CVD method is simpler than the physical vapor deposition (PVD) method such as plasma vapor deposition, vacuum deposition, sputtering, or ion plating, and the like, and the cost of the device itself can be suppressed. Further, in the heating element CVD method, since the gas barrier film is formed by chemical species deposition, a dense film having a high bulk density can be obtained as compared with the wet method.

When a film is formed using the organodecane compound represented by the above formula (Chemical Formula 1) as a material gas, if the plasma CVD method is used, only the oxygen permeability of a 500 ml PET bottle can be suppressed to 2 About 1 point, the practical performance is not sufficient. It is known that if a film containing DLC (Diamond-like Carbon) or SiO _x is formed by a plasma CVD method, the oxygen permeability of a 500 ml PET bottle can be suppressed to less than 1/10, but In the case of being filled with a carbonated beverage, the gas barrier property is lowered accompanying the expansion of the bottle. Specifically, if a 500 ml PET bottle (resin amount 23 g) which is a DLC film or a SiO _x film by a plasma CVD method is filled with 4 GV (gas volume) of carbonated water and maintained at 38 ° C. 5 days, usually PET bottles capacity expansion 18 ~ 21 cm ³ (the case without forming the PET bottles is 22 ~ 26 cm ^3), and the expansion of the oxygen transmission rate is increased to 1.5 to 2.9 times. This is a result of the comprehensive performance of the film damage caused by the expansion and expansion of the PET bottle. On the other hand, when a film is formed using the organic decane compound represented by the above formula (Chemical Formula 1) as a material gas, the oxygen permeability of a 500 ml PET bottle can be obtained by using a heating element CVD method. When it is reduced to, for example, 1/10 or less, sufficient practical performance can be obtained. Further, when the carbonated beverage is filled, the expansion of the bottle can be effectively suppressed, and the gas barrier properties are not substantially lowered. Specifically, when a 500 ml PET bottle (resin amount 23 g) formed by using a heating element CVD method is filled with 4 GV (gas volume) of carbonated water and kept at 38 ° C for 5 days, usually The bottle capacity is only expanded by 13~17 cm ³ (22~26 cm ³ without the film forming bottle), and the oxygen permeability after expansion stops at 1.2~1.3 times.

The gas barrier film 92 thus formed is substantially colorless. In the present specification, the term "substantially colorless" refers to a color difference b ^* value of a color difference in JIS K 7105-1981 "Test method for optical properties of plastics", and a b ^* value of 6 or less. The b ^* value is more preferably 5 or less, and particularly preferably 4 or less. The b ^* value can be obtained by using the number 1. In the number 1, the X, Y or Z system is a tristimulus value.

[Number 1] b*=200[(Y/Y ₀ ) ^1/3 -(Z/Z ₀ ) ^1/3 ]

The gas barrier molded article which is required to have substantially colorless transparency is preferably a barrier property improvement rate (hereinafter referred to as BIF) which is obtained by the number 2 and is 2 or more. More preferably 5 or more, and particularly preferably 8 or more. As a specific example, the oxygen permeability when the container capacity of the gas barrier plastic container is set to 500 ml is preferably 0.0175 cc / container / day or less, more preferably 0.0058 cc / container / day or less, and particularly preferably 0.0035 cc. / container / day below. Further, the film thickness of the gas barrier film 92 and the evaluation method of the oxygen permeability are as shown in the column of the examples.

(Number 2) BIF = [oxygen permeability of a plastic formed body without a film] / [oxygen permeability of a gas barrier plastic molded body]

In the present embodiment, the reason why the oxidizing gas is supplied together with the organodecane compound represented by the formula (Chemical Formula 1) is as follows. When only the organodecane compound represented by the formula (Chemical Formula 1) is supplied, the obtained film mainly contains cerium (Si) and carbon (C) as constituent elements, and the gas barrier property is extremely high. However, the film exhibits a gold color from carbon and is not suitable for applications requiring substantially colorlessness. On the other hand, when an appropriate amount of oxidizing gas is added to the organodecane-based compound represented by the formula (Chemical Formula 1), the obtained film can contain oxygen (O) as a constituent element in addition to Si and C, and is in a gas barrier property. A substantially colorless film is obtained in a practical range. Further, by using Ta or tantalum carbide (TaC _z ) as a heat generating body, a film which is substantially colorless and has gas barrier properties can be formed efficiently and stably.

It is preferable to set the ratio of the content of O in the gas barrier film to the total content of Si, C, and O ({O[at.%]/(Si+C+O)[at.%]}×100). 30~70%. More preferably 40~60%. Since the oxidizing gas as the oxidizing gas is more stable than the oxygen, the gas content in the film can be easily controlled to stably obtain a gas barrier film which is substantially colorless and has high gas barrier properties. Especially excellent.

The gas barrier film may contain, in addition to Si, C, and O, other elements such as a metal element derived from a heating element such as Ta (tan), H (hydrogen), and N (nitrogen).

Since the gas barrier plastic molded article formed by the production method of the present embodiment is substantially colorless and has high gas barrier properties, it is suitable for being easily deteriorated by the influence of oxygen or the like, and is preferably a content of a visually visible content, specifically Examples are packaging applications for food, medicine, pharmaceuticals, and electronic parts.

In the method for producing a gas barrier plastic molded article of the present embodiment, it is preferred to have a regeneration step of supplying the oxidizing gas to the environment and heating the heat generating body 18 after the film forming step. If an organic decane compound is used as the original When the film forming step is repeated using the oxidizing gas as the additive gas, the surface of the heating element 18 is carbonized and the gas barrier properties of the gas barrier film 92 are lowered. As a countermeasure, it is preferable to carry out a regeneration step of the heating element 18 that removes the carbon component from the surface of the heating element 18. The regeneration step of the heating element 18 can easily remove the carbon component from the surface of the heating element 18 by the heat generating body 18 in which the oxidizing gas contacts the heat in the vacuum chamber 6 adjusted to a specific pressure, thereby suppressing the continuous film formation. The gas barrier properties of the gas barrier film 92 are lowered. The regeneration step of the heating element 18 is preferably such that the heating element 18 generates heat after the supply of the oxidizing gas. The oxidizing gas is preferably carbon dioxide. The regeneration step of the heating element 18 can be carried out every one film formation step or after a plurality of film formation steps. Further, the step of regenerating the heating element 18 is preferably performed after the film forming step and after the plastic molded body is taken out from the vacuum chamber 6.

In the regeneration step of the heating element 18, the heating temperature of the heating element 18 is preferably 1900 ° C or higher and 2500 ° C or lower. More preferably, it is 2000 ° C or more and 2400 ° C or less. The heating time is preferably 0.5 times or more and 3.0 times or less of the film formation time. Further, when the oxidizing gas to be supplied is carbon dioxide, the pressure in the vacuum chamber in the regeneration step of the heating element 18 (hereinafter, there is also a case where the vacuum pressure is called regeneration) is preferably 1.3 Pa or more and less than 14 Pa. More preferably, it is 1.4 Pa or more and 13 Pa or less. The vacuum pressure at the time of regeneration is preferably more than 1 time and 9 times with respect to the partial pressure of the material gas 33 in the vacuum chamber at the time of film formation (hereinafter, there is also a case where the partial pressure of the material gas at the time of film formation). Less than the following. When the vacuum pressure at the time of regeneration is less than or equal to the partial pressure of the material gas at the time of film formation, there is a case where the deposition rate of the carbide exceeds the removal rate, and when the film is continuously formed on a plurality of formed bodies, the latter half of the film is formed. Low gas barrier The gas barrier property of the first half of the film. Further, if the vacuum pressure at the time of regeneration exceeds 9 times the partial pressure of the material gas at the time of film formation, there is a case where the carbide is removed and the surface of the heat generating body 18 is oxidized, and the oxidized component is mixed into the gas barrier film or caused by evaporation. Since the heating element 18 is consumed or the like, the gas barrier property of the latter half of the film formation is lowered at the time of continuous film formation. Further, in the regeneration step of the heating element 18, the supply path of the oxidizing gas into the vacuum chamber 6 may be set to be the same as the supply path of the material gas in the film forming step or different from the supply path of the material gas.

Then, regarding the principle of reducing the gas barrier properties of the gas barrier film at the time of repeating the film formation step and the effect of the regeneration step of the heating element 18, the heating element is a metal crucible having a purity of 99.5 mass% and heated to 2000 ° C for 100 consecutive times. The case where the film formation step is repeated is described as an example. Here, the surface of the heating element was analyzed by using a scanning electron microscope (SU1510, manufactured by Hitachi, Ltd.) to observe an elemental composition having a surface depth of 1 μm from the surface of the heating element, and using the energy dispersive X-ray analyzer of the apparatus ( Manufactured by Horiba Manufacturing Co., Ltd., EMAX ENERGY). It was confirmed that the elemental concentration of carbon was less than 1 at.% with respect to film formation, and the maximum increase was 50 at.% after 100 consecutive film formation steps. When this was converted into mass, it was not 0.13 mass% before film formation, and it was 6.2 mass% after repeating film formation process 100 times continuously. The electric resistance of the carbide formed on the surface of the heating element is larger than the electric resistance of the metal crucible forming the central portion of the heating element. Therefore, if the surface of the heating element is carbonized, the surface does not easily rise even when the temperature is applied. As described above, there is a case where it is impossible to ensure a sufficient temperature for the formation of the gas barrier film 92, and a dense film having a high gas barrier property cannot be obtained. Increasing the voltage applied to the heating element 18 to cause heat The surface of the body is also sufficiently heated, whereby in the case of a PET bottle, a gas barrier film 92 capable of improving gas barrier properties by 10 times or more can be formed. However, in the mass production step, the control for adjusting the applied voltage corresponding to the sharp resistance change of the surface of the heating element is complicated. Therefore, by performing the regeneration step of the heating element 18, it is not necessary to apply complicated control of the voltage, and even if the film forming step is continuously performed, a film having a high gas barrier property can be continuously formed.

[Examples]

Hereinafter, the present invention will be described in detail with reference to the embodiments, but the invention is not limited by the examples.

(Example 1)

As a plastic molded body, it is used on the inner surface of a 500 ml PET bottle (having a height of 133 mm, a main body outer diameter of 64 mm, a mouth outer diameter of 24.9 mm, a mouth inner diameter of 21.4 mm, a wall thickness of 300 μm, and a resin amount of 29 g). The film forming apparatus shown in Fig. 1 forms a gas barrier film. The piping from the gas flow rate adjusters 24a to 24c to the gas supply port 16 is composed of a 1/4 inch pipe made of alumina. The PET bottle was housed in the vacuum chamber 6 and depressurized to 1.0 Pa. Then, as the heating element 18, two Φ lines of Φ 0.5 mm and 44 cm in length were used, and a direct current of 25 V was applied to the heating element 18 to generate heat to 2000 °C. Then, the gas flow rate adjuster 24a supplies vinyl decane as a material gas at a flow rate of 50 sccm, and supplies a raw material gas, and uses carbon dioxide as an additive gas from the gas flow rate adjuster 24b at a flow rate of 30. The sccm is supplied in a manner to deposit a film on the inner surface of the PET bottle. The pressure at the time of film formation (full pressure) was set to 6 Pa, and the film formation time was set to 6 seconds. At this time, the partial pressure of the vinyl decane (the partial pressure of the material gas at the time of film formation) was 1.4 Pa. Film thickness It is 30 nm. Further, the film thickness was measured using a stylus profiler (type: α-Step, manufactured by KLA-Tencor Co., Ltd.).

(Example 2)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that the supply amount of the additive gas was set to 10 sccm.

(Example 3)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that the supply amount of the additive gas was set to 20 sccm.

(Example 4)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that the supply amount of the additive gas was set to 50 sccm.

(Example 5)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that the supply amount of the additive gas was set to 100 sccm.

(Example 6)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that oxygen was used instead of carbon dioxide as the additive gas, and the supply amount of the additive gas was set to 5 sccm. Here, the film formation time required to make the film thickness of the gas barrier film to 30 nm was 6 seconds.

(Example 7)

In Example 6, a film was formed on the inner surface of the PET bottle in accordance with Example 6, except that the supply amount of the additive gas was set to 6 sccm.

(Example 8)

In Example 6, except that the supply amount of the additive gas was set to 25 sccm. Further, a film was formed on the inner surface of the PET bottle in accordance with Example 6.

(Example 9)

In Example 6, a film was formed on the inner surface of the PET bottle in accordance with Example 6, except that the supply amount of the additive gas was set to 50 sccm.

(Embodiment 10)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that the film thickness of the film was set to 5 nm.

(Example 11)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that the film thickness of the film was set to 82 nm.

(Embodiment 12)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that a mixed gas of carbon dioxide and oxygen mixed at 9:1 was used instead of carbon dioxide as the additive gas. In Table 1, the supply amount of the additive gas is referred to as the supply amount of the mixed gas of carbon dioxide and oxygen.

(Example 13)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that a mixed gas of vinyl decane and acetylene was mixed in a ratio of 1:1 instead of vinyl decane as a material gas. In Table 1, the supply amount of the material gas is referred to as the supply amount of the mixed gas of vinyl decane and acetylene.

(Example 14)

In Example 1, except that dioxane was used instead of vinyl decane as a raw material gas, and carbon dioxide was used as an additive gas instead of carbon dioxide, and the supply amount of the additive gas was set to 5 sccm, the PET bottle according to Example 1 was used. Inside The surface forms a film. Here, the film formation time required to make the film thickness of the gas barrier film to 30 nm was 8 seconds.

(Example 15)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that the supply amount of the additive gas was set to 3 sccm.

(Embodiment 16)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that the supply amount of the additive gas was set to 130 sccm.

(Example 17)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that oxygen was used instead of carbon dioxide as the additive gas, and the supply amount of the additive gas was set to 2 sccm.

(Embodiment 18)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1, except that oxygen was used instead of carbon dioxide as the additive gas, and the supply amount of the additive gas was set to 65 sccm.

(Embodiment 19)

In Example 1, except that the thermal contact medium was replaced by TaC _x (X=1, the mass ratio of carbon atoms in TaC _x was 6.2% by mass, and the elemental concentration of carbon atoms in TaC _x was 50 at.%). A film was formed on the inner surface of the PET bottle in accordance with Example 1.

(Comparative Example 1)

In Example 1, a film was formed on the inner surface of the PET bottle in accordance with Example 1 except that the additive gas was not supplied.

(Comparative Example 2)

In Example 1, a film was formed on the inner surface of the PET bottle according to Example 1, except that a mixed gas of monomethyl decane and acetylene was mixed in a ratio of 1:1 instead of vinyl decane as a material gas, and no additive gas was supplied.

(Comparative Example 3)

In Comparative Example 2, a film was formed on the inner surface of the PET bottle in accordance with Comparative Example 2, except that carbon dioxide of 30 sccm was supplied as the additive gas.

(Comparative Example 4)

In Example 1, a film was formed on the inner surface of the PET bottle in the same manner as in Example 1 except that the twisted wire was used as the heat generating body, but the film thickness of the film was not increased, and the film thickness was less than 3 nm.

The PET bottles having the gas barrier films of the obtained examples and comparative examples were evaluated by the following methods. The evaluation results are shown in Table 1.

(Transparency evaluation - b ^* value)

The b ^* value is measured by using a 60 Φ integrating sphere matching device (infrared, visible, and near infrared rays) manufactured by the company on a U-3900 self-recording spectrophotometer. The detector uses an ultra-high sensitivity photomultiplier tube (R928: for ultraviolet light and visible light) and a cooled PbS (for near-infrared region). The measurement wavelength was measured in the range from 240 nm to 840 nm. The measurement position was set to be 60 mm from the bottom of the PET bottle. The transmittance measurement of only the gas barrier film can be calculated by measuring the transmittance of the PET bottle, but the b ^* value of the present embodiment is directly expressed as a form including the absorption rate of the PET bottle. Further, the relationship between b ^* and visual observation in the present invention is roughly as shown in Table 2. The b ^* value of the PET bottle without film formation is in the range of 0.6 to 1.0. The criteria for the evaluation of transparency are as follows.

Judgment criteria for transparency evaluation: ◎: b ^* value is 2 or less (practical level), ○: b ^* value exceeds 2 and is 4 or less (practical level), and Δ: b ^* value exceeds 4 and is 6 or less (minimum practical) Horizontal), ×: b ^* value exceeds 6 (not practical level).

(Gas Resistance Evaluation - BIF)

BIF is the value of the oxygen permeability of the PET bottle obtained in the example or the comparative example as the "oxygen permeability of the gas barrier plastic molded body" in the number 2, and the oxygen of the PET bottle which is not formed into a film is worn. Permeability as "plastic film without film formation" Calculated by the oxygen permeability of the body. Oxygen permeability was measured using an oxygen permeability measuring apparatus (type: Oxtran 2/20, manufactured by Modern Control Co., Ltd.) under the conditions of 23 ° C and 90% RH, and was adjusted from the start of measurement for 24 hours from the start of the measurement. After 72 hours, the value. Further, the PET bottle which did not form a film had an oxygen permeability of 0.0350 cc / container / day. The criteria for determining the gas barrier properties are as follows.

Judgment criteria for gas barrier evaluation: ◎: BIF is 8 or more (practical level), ○: BIF is 5 or more and less than 8 (practical level), and Δ: BIF is 2 or more and less than 5 (lowest practical level). ×: BIF is less than 2 (not practical level).

(Comprehensive judgment)

In the case of the above-mentioned transparency determination and gas barrier determination, none of the items of the above-mentioned transparency determination and gas barrier determination is recorded as ○ as a practical level, and × as a non-practical level in any of the items. Recorded as ×.

As shown in Table 1, the films of Examples 1 to 19 have a degree of coloration which is a practical level and is a level which can be said to be substantially colorless. Further, the films of Examples 1 to 19 are all films having gas barrier properties. The BIF of Examples 1 to 3 is 9 or more, and the b ^* value is 3 or less, and is excellent in gas barrier properties and transparency. Among them, in Examples 1 to 3, Example 1 had the smallest b ^* value and particularly high transparency. Although the b ^* values of Examples 4 and 5 are 2 or less and the transparency is further preferable, the BIF is less than 5, and the gas barrier properties are lower than those of Examples 1 to 3. In Examples 6 to 9, since oxygen gas was used as the oxidizing gas, the amount of change in the amount of supply of BIF to the oxidizing gas was sharper than in Examples 1 to 5 in which carbon dioxide gas was used as the oxidizing gas. From this, it was confirmed that carbon dioxide as an oxidizing gas is superior to oxygen in terms of control.

In Example 10, since the film thickness of the gas barrier film was thinner than that of Example 1, the gas barrier property was lower than that of Example 1, but the transparency was superior to that of Example 1. In the eleventh embodiment, since the film thickness of the gas barrier film was thicker than that of the first embodiment, the transparency was lower than that of the first embodiment, but the gas barrier property was higher than that of the first embodiment. Example 12 uses a mixed gas of an oxidizing gas as an additive gas but can form a film having a practical level. In Example 13, a person who mixed the auxiliary material gas was used as the material gas, but a film having a practical level was obtained. In Example 14, dioxane was used as a material gas, but a practical level film was obtained. When Comparative Example 6 and Example 14 were compared, the time required to form the same film thickness was as short as in Example 6, and it was confirmed that vinyl decane was more effective in forming film than dioxane.

Comparing Example 19 with Example 1, since substantially the same transparency and gas barrier properties were obtained, it was confirmed that strontium carbide is a heat generating body which is also useful as ruthenium.

In Comparative Example 1, since the additive gas was not supplied, the chromaticity was an unpractical level. In Comparative Examples 2 and 3, since an organic decane-based compound other than the organodecane-based compound represented by (Chemical Formula 1) was used as a material gas, BIF was not practical. In Comparative Example 4, since the twisted wire was used as the heat generating body, BIF was not practical. The reason is considered to be that the film formation efficiency is poor and the film thickness of the gas barrier film cannot be increased.

Then, a test for confirming the effect of the regeneration step of the heating element 18 was performed.

(Embodiment 20)

The film formation was carried out 100 times in accordance with Example 1, and the regeneration step of the heating element 18 was carried out every time the film formation was completed. In each regeneration step, when the pressure in the vacuum chamber 6 reaches a vacuum pressure of 1.0 Pa, CO _{2 is} supplied as an oxidizing gas to the vacuum chamber 6 so that the vacuum pressure becomes 12.5 Pa (the partial pressure of the material gas at the time of film formation is 1.4 Pa, therefore 9 times its vacuum pressure, the heating element 18 was heated at 2000 ° C for 6 seconds.

(Example 21)

The film formation was carried out 100 times in accordance with Example 1, and the regeneration step of the heating element 18 was carried out every 10 times of film formation. Each regeneration step was carried out under the same conditions as in Example 20 except that the heating time of the heating element 18 was set to 60 seconds.

(Example 22)

Film formation was carried out 100 times in accordance with Example 19, and the regeneration step of the heating element 18 was carried out every time the film formation was completed. Each regeneration step was carried out under the same conditions as in Example 20.

(Example 23)

Film formation was carried out 100 times in accordance with Example 19, and the regeneration step of the heating element 18 was carried out every 10 times of film formation. Each regeneration step was carried out under the same conditions as in Example 21.

(Example 24)

In the embodiment 20, the same as in the embodiment 20 except that the CO _{2 is} supplied to the vacuum chamber 6 so that the vacuum pressure becomes 1.4 Pa (the vacuum pressure of 1.0 Pa of the partial pressure of the material gas at the time of film formation). The regeneration step of the heating element 18 is performed under the conditions.

(Embodiment 25)

In Example 20, except that the CO ₂ is supplied to the vacuum chamber 6 so that the vacuum pressure became 1.3 Pa (when the film-forming raw material gas of a partial pressure of 1.4 Pa vacuum pressure of 0.93 times) than, the same as in Example 20 The regeneration step of the heating element 18 is performed under the conditions.

(Reference example 1)

In Example 20, except that the CO ₂ is supplied to the vacuum chamber 6 so that the vacuum pressure became 14 Pa (feed time points of the deposition gas pressure of 1.4 Pa vacuum pressure of 10.0 times) than, the same as in Example 20 The regeneration step of the heating element 18 is performed under the conditions.

(Reference example 2)

The film formation was carried out 100 times in accordance with Example 1, and the regeneration step of the heating element 18 was not performed.

(Reference Example 3)

The film formation was carried out 100 times in accordance with Example 19, and the regeneration step of the heating element 18 was not performed.

(BIF measurement)

With respect to Examples 20 to 25 and Reference Examples 1 to 3, the BIF of the first and 100th film formation was measured. The measurement method and the criterion of the BIF are referred to as the method described in "Gas Resistance Evaluation - BIF". The measurement result of BIF is shown at 3.

As can be seen from Fig. 3, in the examples 20 to 25, the first and the 100th BIFs are all practical levels. In particular, in Examples 20 to 24, there was no significant difference in gas barrier properties between the first and the 100th film formation, and the 100th time The BIF is 8 or more. In Example 25, since the vacuum pressure at the time of regeneration was lower than the partial pressure of the material gas at the time of film formation, the BIF of the 100th time was 5.8, but the practical level was maintained. On the other hand, in Reference Example 1 to Reference Example 3, the gas barrier properties were good at the time of film formation in the first time, but the gas barrier properties were largely lowered at the time of film formation at the 100th time. In the reference example 1, the step of regenerating the heating element 18 was carried out. However, it is considered that the vacuum pressure at the time of regeneration is too high, so that the surface of the heating element is oxidized, and the gas barrier properties after continuous film formation are lowered. From the above, it was confirmed that the film formation adaptability was improved by performing the regeneration step of the heating element.

[Industrial availability]

The gas barrier plastic molded article of the present invention is suitable for use in packaging materials. Moreover, the gas barrier container including the gas barrier plastic molded article of the present invention is suitable for use in a beverage container for water, tea beverage, refreshing beverage, carbonated beverage, fruit juice beverage, and the like.

6‧‧‧vacuum chamber

8‧‧‧Vacuum valve

11‧‧‧Plastic containers

12‧‧‧Reaction room

13‧‧‧ lower chamber

14‧‧‧O-ring

15‧‧‧Upper chamber

16‧‧‧ gas supply port

17‧‧‧Material gas flow path

17x‧‧‧ gas ejection hole

18‧‧‧heating body

19‧‧‧Wiring

20‧‧‧heating power supply

21‧‧‧ mouth of plastic container

22‧‧‧Exhaust pipe

23‧‧‧Material gas supply pipe

24a, 24b, 24c‧‧‧ flow adjusters

25a, 25b, 25c, 25d‧‧‧ valves

26a, 26b‧‧‧ Connections

27‧‧‧Cooling water flow path

28‧‧‧ Inside the vacuum chamber

29‧‧‧Cooling device

30‧‧‧Case including transparent body

33‧‧‧Material gases

34‧‧‧Chemical species

35‧‧‧Insulated ceramic components

40a‧‧‧Material tank

41a‧‧‧ starting materials

42a, 42b, 42c‧‧‧ gas cylinders

90‧‧‧ gas barrier plastic molded body

91‧‧‧plastic molded body

92‧‧‧ gas barrier film

100‧‧‧ film forming device

Fig. 1 is a schematic view showing one form of a film forming apparatus.

Fig. 2 is a cross-sectional view showing an example of a gas barrier plastic molded body of the embodiment.

Fig. 3 is a view showing the first and the 100th BIF of the film formation in the confirmation test of the heating step of the heating element.

Claims (8)

A method for producing a gas barrier plastic molded body, which is a method for producing a gas barrier plastic molded body in which a gas barrier film is formed on a surface of a plastic molded body, and is characterized by comprising the following film forming step: in the above plastic molded body On the surface, an organic decane-based compound represented by the general formula (Chemical Formula 1) is used as a main raw material gas, and an oxidizing gas is used as an additive gas, and a heating element containing tantalum (Ta) as a main constituent element is used. On the other hand, the gas barrier film is formed, and in the case of H ₃ Si-C _n -X, n is 2 or 3, and X is SiH ₃ , H or NH ₂ . The method for producing a gas barrier plastic molded article according to claim 1, wherein the organodecane compound is vinyl decane. The method for producing a gas barrier plastic molded article according to claim 1 or 2, wherein the oxidizing gas contains carbon dioxide. The method for producing a gas barrier plastic molded article according to claim 3, wherein a mixing ratio of the carbon dioxide to the organic decane-based compound is from 6:100 to 260:100. The method for producing a gas barrier plastic molded article according to claim 1 or 2, wherein the oxidizing gas contains oxygen, and a mixing ratio of the oxygen gas to the organic decane-based compound is 4:100 to 130:100. The method for producing a gas barrier plastic molded article according to claim 1, wherein the plastic molded body is a film, a sheet or a container. The method for producing a gas barrier plastic molded article according to claim 1, wherein the heat generating body is a metal ruthenium, a ruthenium-based alloy or tantalum carbide. The method for producing a gas barrier plastic molded article according to claim 1, wherein after the film forming step, a regeneration step of supplying a oxidizing gas to the environment and heating the heat generating body is performed.