JP4954679B2 - Barrier film-coated plastic container manufacturing method and manufacturing apparatus thereof - Google Patents

Description

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

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

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

Japanese Patent No. 2788412

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

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

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

  In addition, since the hot wire method is vacuum deposition at a high vacuum, it takes a large exhaust facility and a long exhaust time to realize a high degree of vacuum. Furthermore, since the vapor deposition material diffuses in a high vacuum, the diffusion material has a high degree of straightness and is difficult to go around. Therefore, there is a problem that it is difficult to form a uniform film on a three-dimensional object.

  Therefore, the present invention has been made to solve the above-described conventional problems. That is, the object of the present invention is to apply a catalytic chemical vapor deposition method and a hot wire method to form a gas barrier thin film that is safe and high speed and is not damaged by plasma at a low temperature in a three-dimensional plastic container. It is possible to provide an inexpensive method for producing a coated plastic container that can be operated in a manufacturing apparatus that does not require expensive equipment as compared with a plasma CVD film forming apparatus. Here, the object of the present invention is more specifically, as a gas barrier thin film, a metal species-containing DLC thin film that has good adhesion to plastic, a high film formation rate, and a high barrier property. It is providing the manufacturing method of the plastic container which formed into a film.

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

  The present inventor has eagerly developed to solve the above-mentioned problems, and uses both a catalyst wire and a heating wire, and the catalyst wire decomposes the carbon source material gas as a thermal catalyst and becomes DLC. In addition, the metal wire containing the DLC thin film as the barrier film has good adhesion by supplying the metal species to be contained in the DLC by volatilizing the vapor of the component metal as a hot wire to the heating wire. The inventors have found that a film can be formed and completed the present invention.

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

  The catalyst wire is a wire formed of a metal catalyst body that is not substantially volatilized by itself and can decompose the raw material gas into chemical species by catalytic chemical reaction.

The manufacturing method of the barrier film-coated plastic container according to the present invention includes a pressure adjusting step in which the inside of the vacuum chamber containing the plastic container is set to a predetermined pressure equal to or lower than the atmospheric pressure, and a catalyst wire disposed inside the vacuum chamber. A step of energizing and generating heat to form a thermal catalyst, a step of energizing a heating wire disposed in the vacuum chamber to generate heat and forming a hot wire, and a carbon source in the vacuum chamber Supplying a raw material gas, blowing the carbon source raw material gas onto the thermal catalyst body to decompose the carbon source raw material gas to generate chemical species, and volatilizing a metal species from the hot wire, Film formation for forming a metal species-containing DLC thin film by causing the chemical species and the metal species to reach at least one of an inner surface and an outer surface And extent, was closed, the in the film forming step, by reaching the chemical species and the metal species on the surface of the plastic container at the same time, and forming a composite film of the DLC and the metal species. By forming a composite thin film of DLC and a metal species, it is possible to impart translucency / light-shielding properties and coloration due to the metal species.

  In the method for producing a barrier film-coated plastic container according to the present invention, the catalyst wire is a wire mainly composed of tungsten or a nickel-chromium alloy, and the heating wire is molybdenum, palladium, silver, carbon steel, A wire containing titanium, zirconium or hafnium is preferred. Wire mainly composed of tungsten or nickel-chromium alloy can efficiently decompose carbon source gas such as methane gas by catalytic chemical reaction, and contains molybdenum, palladium, silver, carbon steel, titanium, zirconium or hafnium. By energizing and generating heat, the wires easily volatilize their metal species and can be supplied to the substrate as a vapor deposition component.

  In the method for manufacturing a barrier film-coated plastic container according to the present invention, the plastic container is carried into the vacuum chamber via a differential pressure mechanism, and the plastic container is installed in a transport path in the vacuum chamber. A step of being transported on the transport path without contacting the catalyst wire and the heating wire, and a step of unloading the plastic container out of the vacuum chamber via a differential pressure mechanism. Furthermore, it is preferable to have. It is also possible to mass-produce plastic containers coated with a metal species-containing DLC thin film.

An apparatus for manufacturing a barrier film-coated plastic container according to the present invention includes a vacuum chamber that houses a plastic container, an exhaust pump that evacuates the vacuum chamber, a catalyst wire disposed inside the vacuum chamber, A heater power supply for a thermal catalyst that supplies power to the catalyst wire, a heating wire disposed inside the vacuum chamber, a heater power supply for the hot wire that supplies power to the heating wire, and the vacuum chamber source gas supply means for supplying a raw material gas, was perforated in the internal space or outer space, or space both arrangements plastic containers within, a heater power source for the said heater power source heat catalyst hot wire at the same time It is characterized by supplying electric power .

  According to the present invention, it is possible to deposit a gas barrier thin film on a plastic container surface at a low temperature, which is safe and high speed and is not damaged by plasma. In addition, it is possible to manufacture an inexpensive barrier film-coated plastic container that can be operated in a manufacturing apparatus that does not require expensive equipment as compared with a plasma CVD film forming apparatus. Here, when applying both the catalytic chemical vapor deposition method and the hot wire method, the film is formed not in a high vacuum but in a low vacuum of about 1 to 100 Pa. The raw material also wraps around the object, and it becomes possible to form a uniform film. And the metal seed | species containing DLC thin film which is a barrier film has favorable adhesiveness with respect to a plastics, and has high barrier property. Furthermore, the translucency / light-shielding property and coloration can be easily controlled with a relatively high degree of freedom.

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

(First form: film formation on the inner surface of the container)
First, a film forming apparatus according to a first embodiment capable of forming an oxide thin film on the inner surface of a container will be described. 2A and 2B are schematic views showing the film forming apparatus according to the first embodiment, where FIG. 2A is a wire having a linear shape, FIG. 2B is a wire having a coil spring shape, and FIG. 2C is a zigzag wire. In the case of shape. 2B and 2C are partial enlarged views of the source gas supply pipe 23. FIG. Note that “FIG. 2” will be described as “FIG. 2A” unless otherwise specified. A film forming apparatus 100 shown in FIG. 2 includes a vacuum chamber 6 that accommodates a plastic container 11, an exhaust pump (not shown) that evacuates the vacuum chamber 6, and a catalyst wire disposed inside the vacuum chamber 6. 18X, a heater power source 20X for the thermal catalyst body that supplies power to the catalyst wire 18X, a heating wire 18Y disposed inside the vacuum chamber 6, and a hot wire heater that supplies power to the heating wire 18Y A power source 20Y, and source gas supply means for supplying a source gas such as a carbon source source gas into the internal space of the plastic container 11 disposed in the vacuum chamber 6. Here, the source gas supply means is specifically a source gas supply pipe 23 formed of an insulating and heat-resistant material. The catalyst wire 18 </ b> X and the heating wire 18 </ b> Y are both supported by the raw material gas supply pipe 23, but the heating wire 18 </ b> Y is illustrated in the vicinity of the raw material gas supply pipe 23 for ease of illustration. In FIGS. 2B and 2C, the heating wire 18Y is supported by the source gas supply pipe 23, but the heating wire 18Y is not shown for ease of illustration. That is, in FIG. 2B, the description of the coil spring-shaped heating wire 18Y is omitted, and in FIG. 2C, the description of the zigzag-shaped heating wire 18Y is omitted.

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

  The inside of the vacuum chamber 6, particularly the inside of the lower chamber 13, has an inner surface 28 that is a black inner wall or an inner surface to prevent reflection of light emitted with the heat generated by the catalyst wire 18 </ b> X and the heating wire 18 </ b> Y. It is preferable to have irregularities with a surface roughness (Rmax) of 0.5 μm or more. The surface roughness (Rmax) is measured using, for example, a surface roughness measuring device (DEKTAX 3 manufactured by ULVAC TECHNO CORPORATION). In order to make the inner surface 28 a black inner wall, there are a plating process such as black nickel plating and black chrome plating, a chemical film treatment such as radiant and black dyeing, or a method of coloring by applying a black paint. Furthermore, it is preferable to provide a cooling means 29 such as a cooling pipe through which cooling water is flowed inside (not shown) or outside (FIG. 2) the vacuum chamber 6 to prevent the temperature of the lower chamber 13 from rising. Among the vacuum chambers 6, the lower chamber 13 is particularly targeted when the catalyst wire 18 </ b> X and the heating wire 18 </ b> Y are inserted into the plastic container 11 and are just accommodated in the inner space of the lower chamber 13. Because. By preventing the reflection of light and cooling the vacuum chamber 6, the temperature rise of the plastic container 11 and the accompanying thermal deformation can be suppressed. Further, when a chamber 30 made of a transparent body through which the radiated light generated from the energized catalyst wire 18X and the heating wire 18Y can pass, for example, a glass chamber, is disposed inside the lower chamber 13, the glass made in contact with the plastic container 11 is made. Since the temperature of the chamber does not easily rise, the thermal influence on the plastic container 11 can be further reduced.

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

  The source gas supply pipe 23 may be configured as follows as another form (not shown). That is, the source gas supply pipe is a double pipe, the outer pipe is used as a source gas flow path, and a hole, preferably a plurality of holes, is formed in the side wall of the outer pipe. On the other hand, the inner pipe of the double pipe of the source gas supply pipe is formed by a dense pipe, and the cooling water flows as a cooling water flow path. The catalyst wire 18X and the heating wire 18Y are wired along the side wall of the source gas supply pipe, but the holes provided in the side wall of the outer pipe are provided in the catalyst wire 18X and the heating wire 18Y along the side wall. The carbon source material gas passed through comes into contact. The carbon source material gas is efficiently decomposed into chemical species by the catalyst wire 18X that has become a thermal catalyst.

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

  The catalyst wire 18X promotes the decomposition of a carbon source material gas such as methane in the catalytic chemical vapor deposition method. In the present embodiment, the catalyst wire 18X is preferably, for example, a W wire or a nickel-chromium alloy wire (trade name: Nichrome wire) from the viewpoint of decomposition efficiency of a carbon source material gas such as methane. Since it has conductivity, it becomes possible to generate heat by energization. The catalyst wire 18 </ b> X is formed in a wiring shape, and the catalyst wire 18 </ b> X is connected to a connection portion 26 a provided below the fixed portion in the upper chamber 15 of the source gas supply pipe 23 and serving as a connection portion between the wire 19 and the wire 18. One end is connected. And it is supported with the insulating ceramic member 35 provided in the gas blowing hole 17x which is a front-end | tip part. Further, the other end of the catalyst wire 18X is connected to the connection portion 26b by folding. Thus, since the catalyst wire 18X is supported along the side surface of the raw material gas supply pipe 23, the catalyst wire 18X is disposed so as to be positioned substantially on the main axis of the internal space of the lower chamber 13. FIG. 2A shows the case where the catalyst wire 18X is disposed along the periphery of the source gas supply pipe 23 so as to be parallel to the axis of the source gas supply pipe 23. As described above, after spirally wound around the side surface of the source gas supply pipe 23 and supported by the insulating ceramics 35 fixed in the vicinity of the gas blowing hole 17x, it may be folded back toward the connecting portion 26b. Here, the catalyst wire 18 </ b> X is fixed to the source gas supply pipe 23 by being hooked on the insulating ceramic 35. 2A shows the case where the catalyst wire 18X is disposed outside the gas blowing hole 17x in the vicinity of the gas blowing hole 17x of the source gas supply pipe 23. FIG. As a result, the carbon source material gas such as methane blown out from the gas blowing holes 17x easily comes into contact with the catalyst wire 18X, and therefore the carbon source material gas can be efficiently decomposed. Here, it is preferable that the catalyst wire 18 </ b> X is disposed slightly apart from the side surface of the source gas supply pipe 23. This is to prevent a rapid temperature rise of the source gas supply pipe 23. Moreover, the opportunity of contact with the carbon source raw material gas blown out from the gas blowing holes 17x and the carbon source raw material gas in the reaction chamber 12 can be increased. The outer diameter of the source gas supply pipe 23 including the catalyst wire 18X needs to be smaller than the inner diameter of the mouth portion 21 of the plastic container. This is because the source gas supply pipe 23 including the catalyst wire 18X is inserted from the mouth portion 21 of the plastic container. Therefore, if the catalyst wire 18X is separated from the surface of the raw material gas supply pipe 23 more than necessary, the catalyst gas 18X is easily contacted when the raw material gas supply pipe 23 is inserted from the mouth portion 21 of the plastic container. The lateral width of the catalyst wire 18X is suitably 10 mm or more and (inner diameter -6 of the mouth part -6) mm or less in consideration of the positional deviation when inserted from the mouth part 21 of the plastic container. Here, the inner diameter of the mouth portion 21 is approximately 21.7 to 39.8 mm.

  The upper limit temperature when the catalyst wire 18X generates heat is preferably set to be equal to or lower than the temperature at which the wire softens. The temperature at which the thermocatalyst is operated varies depending on the material of the wire and is preferably, for example, 1600 to 2000 ° C., more preferably 1800 to 2000 ° C. if it is a W wire. If it is a nickel-chromium alloy wire, it is preferable that it is 800-1200 degreeC, for example, and it is more preferable that it is 1000-1100 degreeC.

  Further, the catalyst wire 18X may have a portion obtained by processing a wire into a coil spring shape as shown in FIG. 2B in order to increase the chance of contact with a carbon source material gas such as methane. preferable. The coil spring shape includes not only a cylindrical shape but also a conical shape, a barrel shape, or a hook shape, and further includes an unequal pitch shape in which the pitch between these windings is changed. Moreover, you may have the part which processed the wire into the zigzag line shape as shown in FIG.2 (c). Or you may have the part which processed the wire into the wavy line shape (not shown). In any of these forms, the catalyst wire 18X is preferably disposed along the blowing direction of the carbon source material gas such as methane. As a result, the opportunity for the carbon source material gas 33 such as methane to come into contact with the catalyst wire 18X increases.

  The heating wire 18Y is energized to generate heat to be a hot wire, thereby volatilizing a metal component constituting the wire and supplying a metal type vapor. The heating wire 18Y preferably contains a metal or a metal, for example, Mo wire, Pd wire, Ag wire, carbon steel wire, Ti wire, Zr wire, or Hf wire. Since it has conductivity, it becomes possible to generate heat by energization. The heating wire 18Y is formed in a wiring shape, and is fixed to the raw material gas supply pipe 23 by the same method as the catalyst wire 18X. As a result, the carbon source raw material gas such as methane blown out from the gas blowing holes 17x easily comes into contact with the heating wire 18Y, and thus the volatilized metal species are carried to the surface of the plastic container 11 by the viscous flow of the carbon source raw material gas. . At this time, if it is in a high vacuum, the volatilized metal species go straight and reach the surface of the plastic container 11 because of the long mean free process, but the pressure is about 1 to 100 Pa due to the presence of the carbon source material gas. Therefore, the carbon source gas becomes a viscous flow and carries the volatilized metal species. Therefore, the volatilized metal species are supplied to the surface of the three-dimensional plastic container 11 well, so that the uniformity of the barrier film is improved.

  The upper limit temperature when the heating wire 18Y is heated is preferably set to a temperature equal to or lower than the temperature at which the wire softens. However, when supplying the vapor source of the metal species from the substance carried on the wire or the applied substance, it is preferable to set the melting point of these substances below. Accordingly, the temperature at which the hot wire is operated varies depending on the material of the wire and is Mo, for example, preferably 1000 to 2600 ° C., more preferably 1200 to 2400 ° C. If it is Pd, it is preferable that it is 1000-1500 degreeC, for example, and it is more preferable that it is 1100-1200 degreeC. If it is Ag, it is preferable that it is 700-900 degreeC, for example, and it is more preferable that it is 800-840 degreeC. If it is carbon steel, it is preferable that it is 1100-1400 degreeC, for example, and it is more preferable that it is 1200-1300 degreeC. If it is Ti, it is preferable that it is 1300-1600 degreeC, for example, and it is more preferable that it is 1400-1550 degreeC. If it is Zr, it is preferable that it is 1500-1800 degreeC, for example, and it is more preferable that it is 1500-1650 degreeC. If it is Hf, it is preferable that it is 1500-2200 degreeC, for example, and it is more preferable that it is 1800-2000 degreeC.

  The wire shape of the heating wire 18Y may be the same shape as the catalyst wire 18X (for example, FIGS. 2B and 2C). As a result, the surface area of the heating wire 18Y can be increased, and the direction of the volatilization of the metal species can be made uniform in all directions rather than in a specific direction.

  About the fixing method of the source gas supply pipe | tube 23 of the wire 18X for a catalyst, and the wire 18Y for a heating, you may make it as follows as another form not shown. That is, the raw material gas supply pipe is a double pipe, and the outer pipe is formed of a porous pipe having a porosity of 10 to 40% using a raw material gas flow path. The catalyst wire 18X and the heating wire 18Y may be directly wound around the porous outer tube. The stability of the fixing of the catalyst wire 18X and the heating wire 18Y is improved, and the carbon source material gas such as methane is also released from the side wall of the outer tube together with the gas blowing holes. The efficiency is improved, and the metal species volatilized from the heating wire 18Y is efficiently transported by the carbon source material gas blown out. In this case, the inner pipe of the double pipe of the source gas supply pipe is formed by a dense pipe, and the cooling water flows as a cooling water flow path.

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

  The catalyst power wire 18 </ b> X is connected to the heater power source 20 </ b> X for the thermal catalyst through the connection portions 26 a and 26 b and the wiring 19. By supplying electricity to the catalyst wire 18X by the heater power source 20X for the thermal catalyst body, the catalyst wire 18X generates heat and becomes a thermal catalyst body.

  A heater power source 20Y for hot wire is connected to the heating wire 18Y via a connection portion and wiring (not shown). By supplying electricity to the heating wire 18Y by the hot wire heater power source 20Y, the heating wire 18Y generates heat and becomes a hot wire.

  Moreover, since the draw ratio at the time of shaping | molding of the plastic container 11 is small from the opening part 21 of a plastic container to the shoulder of a container, when the catalyst wire 18X and the heating wire 18Y which generate heat | fever to high temperature are arrange | positioned near, it will be by heat Prone to deformation. According to the experiment, the positions of the connection portions 26a and 26b (connection portions of the heating wire 18Y are not shown) that are the connection portions between the wiring 19 and the catalyst wire 18X are 5 mm or more from the lower end of the mouth portion 21 of the plastic container. If it is not separated, the shoulder portion of the plastic container 11 is thermally deformed, and if it is separated beyond 50 mm, it is difficult to form a thin film on the shoulder portion of the plastic container 11. Therefore, the catalyst wire 18X and the heating wire 18Y are preferably arranged such that the upper ends thereof are located 5 to 50 mm below the lower end of the mouth portion 21 of the plastic container. That is, it is preferable that the distance L2 between the connecting portions 26a and 26b and the lower end of the mouth portion 21 is 5 to 50 mm. Thermal deformation of the shoulder portion of the container can be suppressed. The same applies to the connecting portion of the heating wire 18Y.

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

(Second form: film formation on the outer surface of the container)
Next, a film forming apparatus according to a second embodiment capable of forming a gas barrier thin film on the outer surface of the container will be described. FIGS. 4A and 4B are schematic views showing an embodiment of a film forming apparatus according to the second embodiment. FIG. 4A shows a case where the wire is linear, and FIG. 4B shows a case where the wire has a coil spring shape. However, FIG.4 (b) is the schematic of a wire. Note that “FIG. 4” will be described as “FIG. 4A” unless otherwise specified. A film forming apparatus 200 shown in FIG. 4 includes a vacuum chamber 60 that accommodates the plastic container 11, an exhaust pump (not shown) that evacuates the vacuum chamber 60, and a catalyst wire disposed inside the vacuum chamber 60. 18X, a heater power source 20X for a thermal catalyst body that supplies power to the catalyst wire 18X, a heating wire 18Y disposed inside the vacuum chamber 60, and a hot wire heater that supplies power to the heating wire 18Y The power source 20 </ b> Y and source gas supply means for supplying a source gas such as a carbon source source gas into the external space of the plastic container 11 disposed in the vacuum chamber 60. Here, the source gas supply means is specifically a source gas supply pipe 73 formed of an insulating and heat-resistant material. The catalyst wire 18X and the heating wire 18Y are both disposed around the plastic container 11, and FIG. 4 shows the case where the catalyst wire 18X and the heating wire 18Y are wired along the inner wall surface of the vacuum chamber 60. For the sake of simplicity, the catalyst wire 18X is mainly illustrated, and only a part of the heating wire 18Y is illustrated. In FIG. 4B, only the catalyst wire 18X is shown and the heating wire 18Y is omitted, but the heating wire 18Y is the same.

  Further, in the film forming apparatus 200, the opening of the plastic container 11 is fixed by the bottle rotating mechanism 32, and the plastic container 11 is arranged so that the bottom does not contact inside the vacuum chamber 60.

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

  Here, the catalyst wire 18X is connected to the connection portion 79a, which is a connection portion between the wiring 19 and the catalyst wire 18X, and one end thereof. In the film forming apparatus shown in FIG. 4, the catalyst wire 18X is linearly arranged from the inner side surface of the lower chamber 63 to the opposite side surface starting from the connecting portion 79a, and then folded back from there. The other end is connected to the connecting portion 79b by being linearly arranged again on the opposite side surface, bottom surface, and inner side surface. The heating wire 18Y is similarly fixed (however, the connecting portion is not shown). In order to show the positional relationship among the catalyst wire 18X, the heating wire 18Y, and the plastic container 11 at this time, a cross-sectional view taken along line A-A 'is shown in FIG. The catalyst wire 18 </ b> X and the heating wire 18 </ b> Y are arranged at equal intervals on the left and right or top and bottom in the figure so as to surround the plastic container 11. The catalyst wire 18 </ b> X and the heating wire 18 </ b> Y are arranged so that the distance from the outer surface of the plastic container 11 is constant. The uniformity of the film thickness on the outer surface including the bottom of the container is improved. Further, two or more sets of catalyst wires 18X and heating wires 18Y may be arranged. In this case, it is preferable that a plurality of catalyst wires 18X and heating wires 18Y are arranged at rotationally symmetric positions with respect to the main axis of the plastic container. Even in the case shown in FIG. 5, it is possible to improve the uniformity of film formation by forming the plastic container 11 while rotating the plastic container 11 around the main axis by the bottle rotating mechanism 32. In particular, in the case of FIG. 5, since the catalyst wire 18 </ b> X and the heating wire 18 </ b> Y are a set, the effect of improving the uniformity of film formation is high. Although not shown, as another form of arrangement of the catalyst wire 18X and the heating wire 18Y, a form in which the plastic container 11 is wound around the plastic container 11 around the main axis, or There is a form in which a plurality of ring-shaped wires are arranged in parallel on a plurality of cross-sections of the main shaft, respectively. In any form, the uniformity of the film thickness can be improved. Of course, in this embodiment as well, the plastic container 11 may be formed by rotating the plastic container 11 around the main axis by the bottle rotation mechanism 32. Here, when a plurality of sets of the catalyst wires 18X and the heating wires 18Y are arranged, it is preferable that the catalyst wires 18X and the heating wires 18Y are arranged at a distance of 5 cm or more. Without causing thermal damage to the plastic container, the decomposition of the carbon source gas is promoted and the film thickness can be easily obtained. The material of the catalyst wire 18X and the heating wire 18Y may be the same as that of the first embodiment.

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

  One end of the source gas pipe 31 is connected to a gas supply port 66 provided on the bottom surface of the lower chamber 63. A source gas supply pipe 73 is connected to the other end of the source gas pipe 31 and a branch in the middle thereof. In FIG. 4, a plurality of source gas supply pipes 73 are provided, each of which has a gas blowing hole 77x at the tip thereof. A carbon source material gas 33 such as methane flows into the material gas supply pipe 73 through the material gas pipe 31, the gas supply port 66, the flow rate regulator 24a, and the valves 25a to 25b. Thereby, the carbon source material gas 33 such as methane is blown out from the gas blowing holes 77x. All of the gas blowing holes 77x are directed to the outer surface of the plastic container 11, and a carbon source material gas such as methane can be blown to any part of the outer surface. A catalyst wire 18X and a heating wire 18Y are arranged on the outlet side of the gas blowing hole 77x. As a result, a large amount of contact between the catalyst wire 18X and the carbon source material gas such as methane occurs, so that the decomposition of the carbon source material gas into chemical species is promoted. In addition, since the carbon source material gas such as methane blown out from the gas blowing holes 77x easily comes into contact with the heating wire 18Y, the volatilized metal species are brought to the surface of the plastic container 11 by the viscous flow of the carbon source material gas. Carried. At this time, if it is in a high vacuum, the volatilized metal species go straight and reach the surface of the plastic container 11 because of the long mean free process, but the pressure is about 1 to 100 Pa due to the presence of the carbon source material gas. Therefore, the carbon source gas becomes a viscous flow and carries the volatilized metal species. Therefore, the volatilized metal species are supplied to the surface of the three-dimensional plastic container 11 well, so that the uniformity of the barrier film is improved.

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

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

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

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

  The catalyst power source 18 </ b> X is connected to the heater power source 20 </ b> X for the thermal catalyst through the connection portions 79 a and 79 b and the wiring 19. By causing electricity to flow through the catalyst wire 18X by the heater power source 20X for the thermal catalyst body, the catalyst wire 18X generates heat. Also in this embodiment, the operating temperature of the catalyst wire 18X is the same as that when a metal species-containing DLC film is formed as a barrier film on the inner surface of the container.

  A heater power source 20Y for hot wire is connected to the heating wire 18Y via a connection part (not shown) and wiring. By supplying electricity to the heating wire 18Y by the hot wire heater power source 20Y, the heating wire 18Y generates heat. Also in this embodiment, the operating temperature of the heating wire 18Y is the same as that when a barrier film is formed on the inner surface of the container.

  An exhaust pipe 22 communicates with the internal space of the upper chamber 65 via a vacuum valve 8 so that air in the reaction chamber 12 inside the vacuum chamber 60 is exhausted by an exhaust pump (not shown). .

  In any of the film forming apparatuses of the first and second embodiments, the catalyst wire 18X and the heating wire 18Y become a thermal catalyst or a hot wire only by passing an electric current, and a plurality of the catalyst wires 18X and the heating wires 18Y are provided. If a set is prepared, a metal species-containing DLC thin film can be formed in a large amount of plastic containers at once. FIG. 6 is a conceptual diagram of a film forming apparatus for simultaneously forming a metal species-containing DLC thin film on the inner surfaces of a plurality of plastic containers. In FIG. 6, a large number of plastic containers 11 are positioned and arranged in one lower chamber 13, and the catalyst wire 18 </ b> X, the heating wire 18 </ b> Y, and the raw material gas supply pipe 23 are the same as those in FIG. 2. To form a metal species-containing DLC thin film. FIG. 7 is a conceptual diagram of a film forming apparatus for simultaneously forming a metal species-containing DLC thin film on the outer surfaces of a plurality of plastic containers 11. In FIG. 7, a large number of plastic containers 11 are positioned and arranged in one lower chamber 63, and a catalyst wire 18 </ b> X and a heating wire 18 </ b> Y are arranged so as to surround each plastic container 11. After the carbon source material gas such as methane is brought into contact with the catalyst wire 18X from 73, preferably after being brought into contact with both the catalyst wire 18X and the heating wire 18Y, the plastic container 11 is sprayed. Here, the mouth is fixed to the bottle rotation mechanism 32, and a thin film is formed on the outer surface of the plastic container 11 while rotating.

  Further, FIG. 8 is a conceptual diagram of a film forming apparatus for forming a metal species-containing DLC thin film simultaneously on the outer surfaces of a plurality of plastic containers in-line, and (a) is a catalyst wire 18X and a heating wire 18Y. Are arranged in parallel along the transport path, and (b) the catalyst wire 18X and the heating wire 18Y are sequentially disposed in the transport path at intervals. In FIG. 8, the plastic container is moved by the conveyor in the order of the bottle alignment chamber 40, the exhaust chamber 41, the thin film formation chamber 42, the atmospheric leak chamber 43 and the take-out chamber 44 in the vacuum chamber. The outside of the vacuum chamber is under atmospheric pressure, but the thin film forming chamber 42 is kept at a constant pressure reduced by a differential pressure mechanism. The exhaust chamber 41 and the atmospheric leak chamber 43 are included in the differential pressure mechanism.

  In the thin film forming chamber 42 of FIG. 8A, the catalyst wire 18X and the heating wire 18Y are arranged in parallel along the side wall of the chamber. When the plastic container passes through the transfer path in the vacuum chamber, the catalyst wire 18X / heating wire 18Y and the surface of the plastic container approach a desired distance, for example, 5 to 50 mm. In the thin film formation chamber 42, the carbon source material gas is blown out toward the catalyst wire 18X, preferably toward both the catalyst wire 18X and the heating wire 18Y, and the inside of the chamber is used for the carbon source material and heating. Filling with vapor of the metal species derived from the wire 18Y, film formation is performed when the plastic container 11 passes through the thin film formation chamber 42. At this time, since the formed metal species-containing DLC thin film is vapor-deposited simultaneously with the chemical species derived from the carbon source material gas and the metal species derived from the heating wire 18Y, a composite thin film of DLC and the metal species is formed. Is done.

  Further, in the thin film forming chamber 42 of FIG. 8B, a catalyst wire 18X, a heating wire 18Y, and a catalyst wire 18X are sequentially arranged along the side wall of the chamber. When the plastic container passes through the transfer path in the vacuum chamber, the catalyst wire 18X / heating wire 18Y and the surface of the plastic container approach a desired distance, for example, 5 to 50 mm. In the thin film forming chamber 42, the carbon source raw material gas is blown out toward the catalyst wire 18X, and at intervals, a vapor of a metal species derived from the heating wire 18Y is generated, so that the plastic container 11 is in the thin film forming chamber. Film formation is carried out when passing through 42. At this time, the deposited metal species-containing DLC thin film is deposited in the order of chemical species derived from the carbon source material gas, metal species derived from the heating wire 18Y, and chemical species derived from the carbon source material gas. Then, a metal species is deposited on the DLC, and a three-layer laminated thin film in which DLC is further deposited on the metal species is formed.

  Although not shown, if the catalyst wire 18X and the heating wire 18Y are arranged in this order along the side wall of the thin film forming chamber, the formed metal species-containing DLC thin film is a chemical species derived from the carbon source material gas. Since the vapor deposition is performed in the order of the metal species derived from the heating wire 18Y, a two-layer laminated thin film in which the metal species are deposited on the DLC is obtained. Further, if the heating wire 18Y and the catalyst wire 18X are arranged in this order along the side wall of the thin film forming chamber, the formed metal species-containing DLC thin film is converted into a metal species derived from the heating wire 18Y, a carbon source material gas. Therefore, a two-layer laminated thin film in which DLC is deposited on the metal species is obtained.

  In any of the film forming apparatuses of the first and second embodiments, the same vacuum chamber can be used even if the shape of the container is different, a high frequency power source is unnecessary, and a plurality of containers are formed in one vacuum chamber. It can be formed into a film. Thereby, the apparatus becomes cheaper than a film forming apparatus using a high frequency power source.

  In any of the film forming apparatuses of the first form and the second form, it is preferable to provide a container cooling means because the plastic container 11 is easily thermally deformed because the carbon source material gas 33 such as methane becomes hot air. FIGS. 9A and 9B are conceptual diagrams for explaining the container cooling means. FIG. 9A shows a case where a film is formed on the inner surface of the plastic container, and FIG. 9B shows a case where a film is formed on the outer surface of the plastic container. As shown in FIG. 9A, the film forming apparatus of the first form in which the carbon source raw material gas 33 such as methane as hot air is blown into the plastic container 11 is cooled on the outer surface of the plastic container 11. It is preferable to have a container cooling means 51 to which the liquid or gas 50 is applied. The container cooling means 51 is a water tank when the plastic container 11 is immersed in a liquid such as water, and is a shower when the liquid such as water is showered on the plastic container 11. Further, when a gas such as cooling nitrogen gas or cooling carbon dioxide gas is blown into the plastic container 11, it is a blower. The cooling nitrogen gas can be easily obtained by using liquid nitrogen and the cooling carbon dioxide gas by using dry ice. As shown in FIG. 9B, the second type film forming apparatus in which the carbon source raw material gas 33 such as methane serving as hot air is blown toward the outer surface of the plastic container 11 is formed on the inner surface of the plastic container 11. It is preferable to have a container cooling means 51 for applying the cooled liquid or gas 50. The container cooling means 51 is a liquid filling device when filling the plastic container 11 with a liquid such as water, and a blower when blowing a gas such as cooling nitrogen gas or cooling carbon dioxide gas onto the inner surface of the plastic container 11. It is.

  FIG. 10 shows another embodiment of the thin film forming chamber 42 of FIG. On the side wall of the thin film deposition chamber 42, the source gas supply pipes 23 and the container cooling means 51 are alternately arranged along the moving direction of the plastic container 11. The plastic container 11 is moved by a conveyor (conveyance path, not shown) and is rotated. Here, the source gas supply pipe 23 uses the type shown in FIG. The container cooling means 51 uses a type in which cooled nitrogen gas is blown. When the plastic container 11 is moved while being rotated by a conveyor, the metal species derived from the carbon source material gas activated by the wire from the source gas supply pipe 23 and the heating wire supported by the source gas supply pipe 23 Then, the container cooling means 51 sprays the cooled nitrogen gas, and these are alternately performed. At this time, thin film formation proceeds.

  Next, the manufacturing method of the plastic container which coat | covered the metal seed containing DLC thin film which concerns on this embodiment is demonstrated. If the film forming apparatus 100 of FIG. 2 is used, it is possible to coat the metal seed-containing DLC thin film on the inner surface of the plastic container. On the other hand, if the film forming apparatus 200 of FIG. It is possible to coat the outer surface of a plastic container. Since these two film forming methods share the same process, unless otherwise specified, the film forming apparatus 100 shown in FIG. 2 is used as a representative example, and the inner surface of the plastic container is coated with the metal species-containing DLC thin film. The membrane method will be described. Note that the metal seed-containing DLC thin film may be formed on both the inner surface and the outer surface of the plastic container using the film forming apparatus 100 and the film forming apparatus 200.

  The manufacturing method of the plastic container coated with the metal species-containing DLC thin film according to the present embodiment includes a pressure adjustment step in which the inside of the vacuum chamber 6 in which the plastic container 11 is accommodated is set to a predetermined pressure equal to or lower than the atmospheric pressure, Energizing the catalyst wire 18 </ b> X disposed in the heating chamber 18 </ b> X to generate heat as a thermal catalyst body (hereinafter referred to as a thermal catalyst body process) and the heating wire 18 </ b> Y disposed in the vacuum chamber 6. The process of generating heat to generate a hot wire (hereinafter referred to as the hot wire process), supplying the carbon source material gas into the vacuum chamber 6 and blowing the carbon source material gas onto the thermal catalyst to decompose the carbon source material gas The chemical species are generated and the metal species are volatilized from the hot wire 18Y so that the chemical species and the metal species reach the inner surface of the plastic container 11. Having a film forming step of forming a metal species-containing DLC thin film by.

(Attaching the container to the deposition system)
First, a vent (not shown) is opened to open the vacuum chamber 6 to the atmosphere. In the reaction chamber 12, the plastic container 11 is inserted and accommodated from the upper opening of the lower chamber 13 with the upper chamber 15 removed. Thereafter, the positioned upper chamber 15 descends, and the source gas supply pipe 23 attached to the upper chamber 15, the catalyst wire 18 </ b> X and the heating wire 18 </ b> Y fixed to the inside of the plastic container 11 from the mouth portion 21 of the plastic container. Inserted into. Then, the upper chamber 15 is brought into contact with the lower chamber 13 via the O-ring 14, whereby the reaction chamber 12 is made a sealed space. At this time, the distance between the inner wall surface of the lower chamber 13 and the outer wall surface of the plastic container 11 is kept substantially uniform, and the space between the inner wall surface of the plastic container 11 and the catalyst wire 18X / heating wire 18Y. The interval is also kept almost uniform.

  The container according to the present invention includes a container that is used with a lid, a stopper, or a seal, or a container that is used without being used. The size of the opening is determined according to the contents. The plastic container includes a plastic container having a predetermined thickness having moderate rigidity and a plastic container formed by a sheet material having no rigidity. Examples of the filling material in the plastic container according to the present invention include beer, sparkling liquor, carbonated drink, fruit juice drink, and soft drink. Moreover, either a returnable container or a one-way container may be used.

  The resin of the plastic container 11 of the present invention includes polyethylene terephthalate resin (PET), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin (PP), cycloolefin copolymer resin (COC, cyclic olefin copolymer), ionomer. Resin, poly-4-methylpentene-1 resin, polymethyl methacrylate resin, polystyrene resin, ethylene-vinyl alcohol copolymer resin, acrylonitrile resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, polyamideimide resin, polyacetal Examples include resin, polycarbonate resin, polysulfone resin, or tetrafluoroethylene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin. Kill. Among these, PET is particularly preferable.

(Pressure adjustment process)
Next, after closing the vent (not shown), the exhaust pump (not shown) is operated and the vacuum valve 8 is opened, whereby the air in the reaction chamber 12 is exhausted. At this time, not only the internal space of the plastic container 11 but also the space between the outer wall surface of the plastic container 11 and the inner wall surface of the lower chamber 13 is evacuated and evacuated. That is, the entire reaction chamber 12 is exhausted. The pressure in the reaction chamber 12 is reduced until it reaches a required pressure, for example, 1 to 100 Pa, preferably 10 to 100 Pa. This requires an exhaust time at a pressure of less than 1 Pa, and the film formation rate may decrease, resulting in an increase in film formation cost. Moreover, if a pressure higher than 100 Pa is sufficient, impurities increase in the plastic container 11, and a container with a high barrier property cannot be obtained.

(Thermal catalyst process)
Next, the catalyst wire 18X is energized to generate heat above a predetermined temperature to obtain a thermal catalyst. As described above, when the carbon source material gas is methane gas, the predetermined temperature is preferably 1600 to 2000 ° C, and more preferably 1800 to 2000 ° C, when W wire is used. If it is a nickel-chromium alloy wire, it is preferable that it is 800-1200 degreeC, for example, and it is more preferable that it is 1000-1100 degreeC. The catalyst wire 18X is arranged so that the distance from the inner surface of the plastic container 11 is 5 to 50 mm.

(Hot wire process)
Next, the heating wire 18Y is energized to generate heat above a predetermined temperature to obtain a hot wire. The components of the wire can be volatilized and steam can be supplied into the reaction chamber 12. As described above, the predetermined temperature to be operated as a hot wire varies depending on the material of the wire and is Mo, for example, preferably 1000 to 2600 ° C, and more preferably 1200 to 2400 ° C. If it is Pd, it is preferable that it is 1000-1500 degreeC, for example, and it is more preferable that it is 1100-1200 degreeC. If it is Ag, it is preferable that it is 700-900 degreeC, for example, and it is more preferable that it is 800-840 degreeC. If it is carbon steel, it is preferable that it is 1100-1400 degreeC, for example, and it is more preferable that it is 1200-1300 degreeC. If it is Ti, it is preferable that it is 1300-1600 degreeC, for example, and it is more preferable that it is 1400-1550 degreeC. If it is Zr, it is preferable that it is 1500-1800 degreeC, for example, and it is more preferable that it is 1500-1650 degreeC. If it is Hf, it is preferable that it is 1500-2200 degreeC, for example, and it is more preferable that it is 1800-2000 degreeC. Note that the heating wire 18Y is disposed such that the distance from the inner surface of the plastic container 11 is 5 to 50 mm.

(Film formation process)
Thereafter, a carbon source material gas such as methane is supplied at a predetermined flow rate by the gas flow rate regulator 24a. A carbon source material gas such as methane is supplied from the gas blowing hole 17x toward the catalyst wire 18X, preferably the catalyst wire 18X, in the plastic container 11 that has been decompressed to a predetermined pressure via the material gas supply pipe 23. It blows out toward both of the heating wires 18Y. Then, the carbon source material gas such as methane is decomposed into highly active chemical species by the catalyst wire 18 </ b> X and brought into contact with the inner surface of the plastic container 11. At the same time, the metal species volatilized from the hot wire 18Y are brought into contact with the inner surface of the plastic container 11 together with the chemical species. A metal seed-containing DLC thin film is formed on the inner surface of the plastic container 11.

  In the present invention, the carbon source material gas is, for example, alkane gases such as methane, ethane, propane, butane, pentane, hexane, alkene gases such as ethylene, propylene, butyne, and alkadienes such as butadiene, pentadiene, etc. Gases, alkyne gases such as acetylene and methylacetylene, aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene, cycloalkane gases such as cyclopropane and cyclohexane, cyclobenten and cyclohexene Such as cycloalkene gases such as methanol and ethanol, ketone gases such as acetone and methyl ethyl ketone, and aldehyde gases such as formaldehyde and acetaldehyde. Of these, methane gas is preferred.

In addition, as a raw material gas, a gas that does not undergo polymerization but participates in a chemical reaction, such as hydrogen, oxygen, nitrogen, water vapor, ammonia, or CF ₄ , is introduced into the reaction chamber 12 where the exothermic thermal catalyst 18Y exists. Can improve the quality of the gas barrier thin film.

  A dilution gas may be mixed with the source gas. For example, an inert gas such as argon or helium is inert to the chemical reaction during film formation, and can be used to adjust the concentration of the source gas and the pressure in the vacuum chamber.

  In this embodiment, the plastic container 11 may be irradiated with ultraviolet rays at the time of film formation (ultraviolet irradiation means is not shown). It can be used for heating and activation of the plastic container 11.

  In this product embodiment, there are, for example, four forms when roughly classified by the supply method of the chemical species derived from the carbon source material gas and the metal species derived from the heating wire. First, as a first form, there is a form in which a composite thin film of DLC and metal species is formed by simultaneously bringing chemical species and metal species into the surface of the plastic container 11 in the film forming step. According to the first embodiment, a composite thin film in which DLC and metal species are uniformly mixed on the order of nano to micron can be obtained. The composite thin film of DLC and a metal seed | species can provide the translucency / light-shielding property and coloration by a metal seed | species.

  Here, DLC in the metal species-containing DLC thin film is a deposit deposited as DLC when the carbon source raw material gas is decomposed into highly active chemical species by the thermal catalyst and the chemical species reaches the surface of the plastic container. It is. In addition, the metal species is a vapor composed of several to several hundreds of metal clusters or metal oxide fine particles combined with oxygen in the reaction chamber 12 when the heating wire generates heat. In addition, the metal species in the metal species-containing DLC thin film are deposits deposited as metal or metal oxide when the vapor reaches the surface of the plastic container. In the present invention, metals or metal oxides derived from the heating wire are collectively referred to as metal species.

  Next, as a second form, in the film forming process, a form in which a two-layer laminated thin film in which metal species are deposited on DLC is formed on the surface of the plastic container 11 by reaching chemical species and metal species in this order. is there. As a forming method, it is possible to shift the supply timing of the chemical species and the metal species. For example, as described above, the catalyst wire and the heating wire similar to those in FIG. 8B are sequentially arranged along the transport path. This can be achieved by sequentially transporting and forming a plastic container on the transport path of the continuous manufacturing apparatus. A two-layer laminated thin film in which metal species are deposited on DLC has high adhesion because the DLC layer serves as an adhesion layer. Moreover, the translucency / light-shielding property and coloration by a metal seed | species can be provided. Further, this embodiment is suitable for forming a film on the outer surface of a plastic container.

  Next, as a third mode, in the film forming step, a mode in which a two-layer laminated thin film in which DLC is deposited on the metal species is formed on the surface of the plastic container 11 in the order of metal species and chemical species. is there. As a formation method, it is possible by shifting the supply timing of the metal species and the chemical species. For example, as described above, the heating wire and the catalyst wire similar to FIG. This can be done by sequentially transporting and depositing plastic containers on the transport path of the arranged continuous manufacturing apparatus. A two-layer laminated thin film in which DLC is deposited on a metal species has high chemical stability because the chemically stable DLC layer is the outermost layer. Therefore, there is an effect of preventing elution of metal species. Moreover, the translucency / light-shielding property and coloration by a metal seed | species can be provided.

  Next, as a fourth embodiment, in the film forming process, the metal species are deposited on the DLC by reaching the surface of the plastic container 11 in the order of chemical species, metal species, and chemical species, and further on the metal species. There is a form of forming a three-layer laminated thin film in which DLC is deposited. As a formation method, it is possible by shifting the supply timing of the chemical species, the metal species, and the chemical species. For example, as described above, as shown in the apparatus of FIG. 8B, the wire for catalyst, the wire for heating, the catalyst This can be done by sequentially transporting and forming a plastic container on the transport path of a continuous manufacturing apparatus in which wire for operation is sequentially arranged along the transport path. The three-layer laminated thin film has high adhesion and high chemical stability because the lower DLC layer serves as an adhesion layer and the outermost DLC layer serves as a protective layer. Therefore, there is an effect of preventing elution of metal species. Moreover, the translucency / light-shielding property and coloration by a metal seed | species can be provided. In addition, in this invention, it is not limited to the 1st-4th form, You may form the laminated thin film of four or more layers.

  Here, when the metal species is molybdenum or carbon steel, it can be colored blue. When the metal species is palladium or silver, it can be colored gray.

(Finish film formation)
When the thin film reaches a predetermined thickness, the supply of the carbon source material gas 33 such as methane is stopped, the reaction chamber 12 is evacuated again, a leak gas (not shown) is introduced, and the reaction chamber 12 is brought to atmospheric pressure. To do. Thereafter, the upper chamber 15 is opened and the plastic container 11 is taken out. The thickness of the thin film is preferably 5 to 100 nm. According to the above-described embodiment, the upper limit of the film forming speed is 2.5 to 4.0 nm / second, for example. When the oxygen permeability of the plastic container coated with the metal species-containing DLC thin film was measured, it was reduced to 1/3 to 1/18 compared with the uncoated plastic container, and the improvement of the barrier property was confirmed. .

  When the metal species-containing DLC thin film is formed on the outer surface of the plastic container 11, the film is formed in a state where the plastic container 11 is rotated by the bottle rotation mechanism 32 in order to improve the uniformity of the film. Is preferred.

  Next, an embodiment in which mass production is performed in the method for manufacturing a plastic container coated with the metal seed-containing DLC thin film according to the present embodiment will be described. In the method for manufacturing a plastic container coated with the metal species-containing DLC thin film according to the present embodiment, the plastic container 11 is placed inside the vacuum chamber 6 that is set to a predetermined pressure (eg, 1 to 100 Pa) that is equal to or lower than atmospheric pressure in the pressure adjustment step. Although it will be in the accommodated state, in order to achieve this state, a step of bringing the plastic container 11 into the vacuum chamber 6 via a differential pressure mechanism is added. Since the plastic containers 11 are continuously conveyed one after another at predetermined intervals on the conveyance path, it is preferable to use a type having a differential pressure mechanism shown in FIG. 8 for example as a vacuum chamber rather than a batch type. The surface of the plastic container 11 is not in contact with the catalyst wire 18X and the heating wire 18Y, and the plastic container 11 is connected to the catalyst wire 18X and the heating wire 18Y installed in the transport path in the vacuum chamber. On the other hand, a step of transporting on the transport path is added so that the surface of the plastic container 11 approaches a desired distance (for example, 5 to 50 mm). Further, a step of taking out the plastic container after film formation, that is, a step of transporting the plastic container 11 out of the vacuum chamber via a differential pressure mechanism is further added. By adding the above steps, it is possible to efficiently mass-produce plastic containers coated with a metal species-containing DLC thin film.

Example 1
Film formation was performed on the inner surface of a round 500 ml PET bottle as a plastic container 11 using the film formation apparatus 100 shown in FIG. The wall thickness of the container wall was about 0.3 mm. A tungsten wire was used as the catalyst wire 18X, and a molybdenum wire was used as the heating wire 18Y. Methane was used as a carbon source material gas and 80 sccm was supplied. The distance between the catalyst wire 18X / heating wire 18Y and the bottom surface inside the bottle was 30 mm. The distance between the catalyst wire 18X / heating wire 18Y and the inner side surface of the bottle was about 30 mm. A direct current was applied to the catalyst wire 18X to obtain a thermal catalyst at 2000 ° C. A direct current was applied to the heating wire 18Y to obtain a hot wire at 2100 ° C. The pressure in the vacuum chamber 6 during film formation was 6 Pa. The film formation time was 10 seconds. Chemical species and metal species were allowed to reach the plastic surface at the same time. A PET bottle coated with the obtained metal species-containing DLC thin film (composite thin film of DLC and metal species) was defined as Example 1. Example 1 was evaluated as follows.

(Evaluation methods)
(1) Oxygen permeability The oxygen permeability of this container was measured under conditions of 23 ° C. and 90% RH using Oxtran 2/20 manufactured by Modern Control, and was measured 72 hours after the start of nitrogen gas replacement. Was described.
(2) Film thickness The film thickness of DLC was measured using DEKTAK3 manufactured by Veeco.

For Example 1, the oxygen transmission rate was 0.0035 cc / container / day. The film thickness was 25 nm. The thin film was blue. The production conditions and evaluation results are summarized in Table 1.

(Example 2)
Example 2 was carried out in the same manner as in Example 1 except that palladium wire was used as the heating wire and the temperature was 1200 ° C. The film forming conditions and results are shown in Table 1.

(Example 3)
A nickel-chromium alloy wire was used as the catalyst wire, the temperature was 1000 ° C., and the film formation time was 40 seconds. The film forming conditions and results are shown in Table 1.

Example 4
Example 4 was performed in the same manner as in Example 3 except that palladium wire was used as the heating wire, the temperature was 1200 ° C., and the film formation time was 109 seconds. The film forming conditions and results are shown in Table 1.

( Reference Example 5)
Using the film forming apparatus 100 shown in FIG. 2, film formation was performed on the inner surface of the same plastic container as in Example 1. A molybdenum wire was used as the heating wire 18Y. The distance between the heating wire 18Y and the bottom surface inside the bottle was 30 mm. The distance between the heating wire 18Y and the inner side surface of the bottle was about 30 mm. A direct current was applied to the heating wire 18Y to obtain a hot wire at 2100 ° C. The pressure in the vacuum chamber 6 at the time of film formation was set to 6 Pa, and only metal species were vapor-deposited first. The film formation time was 20 seconds. Next, tungsten wire was used as the catalyst wire 18X, and methane was used as the carbon source material gas, and 80 sccm was supplied. The distance between the catalyst wire 18X and the bottom surface inside the bottle was 30 mm. The distance between the catalyst wire 18X and the inner side surface of the bottle was about 30 mm. A direct current was applied to the catalyst wire 18X to obtain a thermal catalyst at 2000 ° C. The pressure in the vacuum chamber 6 at the time of film formation was 6 Pa, and only chemical species was deposited. The film formation time was 5 seconds. By the above operation, film formation was performed by reaching the plastic surface in the order of metal species and chemical species. A PET bottle coated with the obtained metal species-containing DLC thin film (two-layer laminated thin film in which DLC was deposited on the metal species) was used as Reference Example 5. The film forming conditions and results are shown in Table 1.

( Reference Example 6)
Palladium wire used as a heating wire 18Y, and 1200 ° C. hot wire, except the deposition of the metal species forming time as 100 seconds performs a film formation in the same manner as in Reference Example 5 was as in Reference Example 6. The film forming conditions and results are shown in Table 1.

( Reference Example 7)
Catalyzes wire 18X nickel - using chromium alloy wire, a thermal catalyst of 1000 ° C., except that was deposited species the deposition time as 120 seconds performs a film formation in the same manner as in Reference Example 5, Reference Example It was set to 7. The film forming conditions and results are shown in Table 1.

( Reference Example 8)
Reference Example 8 was formed in the same manner as Reference Example 7 except that palladium wire was used as the heating wire 18Y, a hot wire of 1200 ° C. was used, and the metal species was deposited with a film formation time of 100 seconds. The film forming conditions and results are shown in Table 1.

( Reference Example 9)
Using the film forming apparatus 100 shown in FIG. 2, film formation was performed on the inner surface of the same plastic container as in Example 1. Tungsten wire was used as the catalyst wire 18X, methane was used as the carbon source material gas, and 80 sccm was supplied. The distance between the catalyst wire 18X and the bottom surface inside the bottle was 30 mm. The distance between the catalyst wire 18X and the inner side surface of the bottle was about 30 mm. A direct current was applied to the catalyst wire 18X to obtain a thermal catalyst at 2000 ° C. The pressure in the vacuum chamber 6 at the time of film formation was 6 Pa, and only chemical species was deposited. The film formation time was 5 seconds. Next, a molybdenum wire was used as the heating wire 18Y. The distance between the heating wire 18Y and the bottom surface inside the bottle was 30 mm. The distance between the heating wire 18Y and the inner side surface of the bottle was about 30 mm. A direct current was applied to the heating wire 18Y to obtain a hot wire at 2100 ° C. The pressure in the vacuum chamber 6 at the time of film formation was set to 6 Pa, and only metal species was deposited. The film formation time was 20 seconds. By the above operation, film formation was performed by reaching the plastic surface in the order of chemical species and metal species. A PET bottle coated with the obtained metal species-containing DLC thin film (a two-layer laminated thin film in which metal species were deposited on DLC) was used as Reference Example 9. The film forming conditions and results are shown in Table 1.

( Reference Example 10)
Reference Example 10 was formed in the same manner as Reference Example 9 except that palladium wire was used as the heating wire 18Y, a hot wire of 1200 ° C. was used, and the metal species was deposited with a film formation time of 100 seconds. The film forming conditions and results are shown in Table 1.

( Reference Example 11)
Catalyzes wire 18X nickel - using chromium alloy wire, a thermal catalyst of 1000 ° C., except that was deposited species the deposition time as 120 seconds performs a film formation in the same manner as in Reference Example 9, Reference Example It was set to 11. The film forming conditions and results are shown in Table 1.

( Reference Example 12)
Reference Example 12 was formed in the same manner as Reference Example 11 except that palladium wire was used as the heating wire 18Y, a hot wire of 1200 ° C. was used, and the metal seed was deposited with a film formation time of 100 seconds. The film forming conditions and results are shown in Table 1.

( Reference Example 13)
Using the film forming apparatus 100 shown in FIG. 2, film formation was performed on the inner surface of the same plastic container as in Example 1. Tungsten wire was used as the catalyst wire 18X, methane was used as the carbon source material gas, and 80 sccm was supplied. The distance between the catalyst wire 18X and the bottom surface inside the bottle was 30 mm. The distance between the catalyst wire 18X and the inner side surface of the bottle was about 30 mm. A direct current was applied to the catalyst wire 18X to obtain a thermal catalyst at 2000 ° C. The pressure in the vacuum chamber 6 at the time of film formation was 6 Pa, and only chemical species was deposited. The film formation time was 5 seconds. Next, a molybdenum wire was used as the heating wire 18Y. The distance between the heating wire 18Y and the bottom surface inside the bottle was 30 mm. The distance between the heating wire 18Y and the inner side surface of the bottle was about 30 mm. A direct current was applied to the heating wire 18Y to obtain a hot wire at 2100 ° C. The pressure in the vacuum chamber 6 at the time of film formation was set to 6 Pa, and only metal species was deposited. The film formation time was 20 seconds. Next, only the chemical species were again deposited under the same conditions as the deposition of the first chemical species to be the first layer. By the above operation, film formation was performed by reaching the plastic surface in the order of chemical species, metal species, and chemical species. A PET bottle coated with the obtained metal species-containing DLC thin film (a three-layer laminated thin film in which metal species were deposited on DLC and DLC was further deposited on the metal species) was used as Reference Example 13. The film forming conditions and results are shown in Table 1.

( Reference Example 14)
Reference Example 14 was formed in the same manner as Reference Example 13 except that palladium wire was used as the heating wire 18Y, a hot wire of 1200 ° C. was used, and the metal species was deposited with a film formation time of 100 seconds. The film forming conditions and results are shown in Table 1.

( Reference Example 15)
Reference Example 13 except that the catalyst wire 18X is a nickel-chromium alloy wire, is a 1000 ° C. thermal catalyst, the film formation time is 120 seconds, and the first and third layers are vapor-deposited chemical species. In the same manner, a film was formed and used as Reference Example 15. The film forming conditions and results are shown in Table 1.

( Reference Example 16)
Palladium wire used as a heating wire 18Y, and 1200 ° C. hot wire, except the deposition of the metal species forming time as 100 seconds performs a film formation in the same manner as in Reference Example 15 was as in Reference Example 16. The film forming conditions and results are shown in Table 1.

(Examples 17 to 20, Reference Examples 21 to 32)
Instead of the film forming apparatus 100 shown in FIG. 2, using the film forming apparatus 200 shown in FIG. 4, the same metal species-containing DLC thin films as in Examples 1 to 4 and Reference Examples 5 to 16 are removed from the plastic container. It formed into a film on the surface and was set as Examples 17-20 and Reference Examples 21-32 , respectively.

(Comparative Example 1)
The oxygen permeability of the uncoated plastic container was 0.035 cc / container / day.

  When Mo was vapor-deposited as a metal species, the color of the thin film was blue. Moreover, when Pd was vapor-deposited as a metal seed, the color of the thin film was gray. The gas barrier properties were improved in all examples.

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

It is a block diagram of the conventional DLC film forming apparatus. It is the schematic which shows one form of the film-forming apparatus which concerns on a 1st form, (a) when a wire is a linear shape, (b) when a wire is a coil spring shape, (c) is a zigzag wire shape. In the case of The other form of the positional relationship of a wire and a source gas supply pipe was shown. It is the schematic which shows one form of the film-forming apparatus which concerns on a 2nd form, (a) is a case where a wire is linear, (b) is a case where a wire is a coil spring shape. An A-A 'cross-sectional view is shown. It is a conceptual diagram of the apparatus for depositing a gas barrier thin film simultaneously on the inner surfaces of a plurality of plastic containers. It is a conceptual diagram of the apparatus for forming a gas barrier thin film simultaneously on the outer surface of a plurality of plastic containers. It is a conceptual diagram of the film-forming apparatus for forming the metal seed content DLC thin film simultaneously on the outer surface of a plurality of plastic containers in-line, and (a) shows the catalyst wire 18X and the heating wire 18Y along the conveyance path. When both are arranged in parallel, (b) the case where the catalyst wire 18X and the heating wire 18Y are sequentially arranged on the transport path with a gap therebetween. It is a conceptual diagram for demonstrating a container cooling means, (a) is a case where it forms into a film on the inner surface of a plastic container, (b) is a case where it forms into a film on the outer surface of a plastic container. The other form of the thin film formation chamber of FIG. 8 was shown.

Explanation of symbols

1, 12, reaction chamber 1A, carbon source gas inlet 1B, exhaust port 2, external electrode 3, internal electrode 4, high frequency power source 5, 11, plastic container 6, 60, vacuum chamber 8, vacuum valves 13, 63, Lower chamber 14, O-rings 15 and 65, upper chambers 16 and 66, gas supply port 17, source gas flow paths 17x and 77x, gas blowing holes 18X, catalyst wire 18Y, heating wire 19, wiring 20X, thermal catalyst Heater power supply 20Y, hot wire heater power supply 21, plastic container opening 22, exhaust pipes 23 and 73, source gas supply pipe 24a, flow rate regulators 25a and 25b, valves 26a, 26b, 79a and 79b, and connecting section 27 , Cooling water flow path 28, inner surface 29 of the vacuum chamber, cooling means 30, chamber 31 made of a transparent body, source gas pipe 32, bottle rotation mechanism 3 , 34, carbon source material gas 35 such as methane, insulating ceramic member 36, inner tube 40 made of insulating ceramic with an expansion / contraction mechanism, bottle alignment chamber 41, exhaust chamber 42, thin film forming chamber 43, atmospheric leak chamber 44, take-out chamber 50, cooled liquid or gas 51, container cooling means 100, 200, film forming apparatus

Claims (4)

A pressure adjusting step in which the inside of the vacuum chamber containing the plastic container is set to a predetermined pressure below atmospheric pressure;
A step of energizing a catalyst wire disposed inside the vacuum chamber to generate heat to form a thermal catalyst,
A step of energizing a heating wire disposed inside the vacuum chamber to generate heat to form a hot wire;
A carbon source raw material gas is supplied to the inside of the vacuum chamber, the carbon source raw material gas is sprayed on the thermal catalyst body to decompose the carbon source raw material gas to generate a chemical species, and a metal species from the hot wire Forming a metal species-containing DLC thin film by causing the chemical species and the metal species to reach at least one of the inner surface and the outer surface of the plastic container;
I have a,
In the film forming step, a composite thin film of DLC and a metal species is formed by simultaneously bringing the chemical species and the metal species to the surface of the plastic container. .   The catalyst wire is a wire mainly composed of tungsten or a nickel-chromium alloy, and the heating wire is a wire containing molybdenum, palladium, silver, carbon steel, titanium, zirconium or hafnium. The method for producing a barrier film-coated plastic container according to claim 1. The plastic container is carried into the vacuum chamber via a differential pressure mechanism;
The plastic container is transported on the transport path without contacting the catalyst wire and the heating wire installed in the transport path in the vacuum chamber;
Said plastic container, a barrier film manufacturing method of the coated plastic container according to claim 1 or 2, characterized in that it has further a step to be carried out through the differential pressure mechanism into the vacuum chamber outside. A vacuum chamber containing a plastic container;
An exhaust pump for evacuating the vacuum chamber;
A catalyst wire disposed inside the vacuum chamber;
A heater power source for a thermal catalyst body for supplying power to the catalyst wire;
A heating wire disposed inside the vacuum chamber;
A hot wire heater power supply for supplying power to the heating wire;
A raw material gas supply means for supplying a raw material gas to the internal space and / or the external space of the plastic container disposed in the vacuum chamber;
It has a heater power source for the said heater power source heat catalyst hot wire at the same time a barrier film coated plastic container manufacturing apparatus characterized by supplying power.

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