JP5566334B2 - Gas barrier plastic molded body and method for producing the same - Google Patents

Description

  The present invention relates to a gas barrier plastic molding and a method for producing the same.

  It is known that gas barrier properties can be imparted by forming a thin film made of an oxide on the surface of a plastic molded body. A method of laminating a gas barrier thin film mainly composed of an inorganic oxide on the inner surface of a plastic container using a plasma chemical vapor deposition method (plasma CVD method) has been disclosed (for example, see Patent Document 1). Further, a plastic molded article in which an organic metal vapor deposition layer and an oxide layer are sequentially formed on a plastic substrate by a plasma CVD method is disclosed (for example, see Patent Document 2). However, in the method of forming an oxide thin film by plasma CVD, plasma damages the film surface during thin film formation, and the content of water molecules in the thin film tends to increase, and high gas barrier properties can be stabilized in an aqueous solution. It is difficult to obtain a plastic container that can be maintained. Since the raw material gas is made into plasma by high frequency including microwaves and reacted with the surface of the plastic container to form a thin film, a high frequency power supply and a high frequency power matching device are necessary, and the cost of the device must be high. Has the problem of not.

  In order to solve this problem, the present applicant decomposed the raw material gas by contacting the generated heating element with a raw material gas, and after the reaction of the generated chemical species directly or in the gas phase, a thin film is formed on the substrate. Is deposited on the wall surface of the plastic container using a CVD method called a heating element CVD method, a Cat-CVD method or a hot wire CVD method (hereinafter referred to as a heating element CVD method). A technique for forming a silicon (SiOx) thin film or an aluminum oxide (AlOx) thin film has been proposed (see, for example, Patent Document 3).

  In general, an oxide thin film has lower adhesion to a plastic substrate than a carbon film, and the range of applications has been limited. If carbon remains in the oxide thin film, adhesion to the plastic substrate can be improved. However, increasing the residual amount of carbon to improve adhesion has a problem of coloring, and is colorless and transparent, which is considered an advantage of the oxide thin film. Can be lost. Further, as the carbon remaining in the oxide thin film increases, the gas barrier property generally tends to be lowered in the plasma CVD method. Therefore, a technique is known in which a thin film having a large amount of carbon is formed as an adhesion layer between an oxide thin film and a plastic substrate (see, for example, Patent Document 4). In this case, as a result of the thin film component having a high carbon content forming a mixed layer with the plastic substrate, the oxide thin film can be firmly adhered to the plastic substrate. This is because ions in the plasma are electrically attracted to the plastic substrate and react with the plastic substrate while penetrating into the plastic substrate. In principle, all the hydrocarbons and silicon-containing hydrocarbons are removed from the adhesion layer. It can be a source gas.

JP 2005-200043 A WO2008 / 013314 JP 2008-127053 A JP 2006-192858 A

  Up to now, although there has been an examination case of forming a gas barrier thin film having both high gas barrier properties and transparency using a heating element CVD method, unlike the plasma CVD method, high adhesion with a plastic molded body has been demonstrated. There is no disclosure of any knowledge about the film forming method or source gas that can be secured by using the CVD method. In particular, in the heating element CVD method, since plasma is not generated and ions are not present or substantially absent, it is not expected to form a mixed layer with a plastic substrate unlike the plasma CVD method.

  An object of the present invention is to provide a method of forming a gas barrier thin film having high gas barrier properties, transparency, and adhesiveness on the surface of a plastic molded body by using a heating element CVD method.

The method for producing a gas barrier plastic molded body according to the present invention is the method for producing a gas barrier plastic molded body in which a gas barrier thin film having an adhesion layer and a gas barrier expression layer is sequentially formed on the surface of the plastic molded body. on the surface of, in the heating element CVD method, using an organic silane compound represented as the raw material gas by the general formula (formula 1), one of the constituent elements as the adhesion layer is a step 1 of forming a layer which is Si A step 2 of forming a layer containing an oxide containing Al as the gas barrier developing layer on the adhesion layer by a heating element CVD method, and the step 2 forms the gas barrier developing layer. Dimethylaluminum isopropoxide is used as a raw material gas, and at least one metal element of tantalum or molybdenum as a heating element A material comprising using the heat generation temperature of the heat generating member, characterized by a 900-1600 ° C.. By having Step 2, it is possible to express higher gas barrier properties than in the case of Step 1 alone. Step 2 uses dimethylaluminum isopropoxide as a source gas for forming the gas barrier development layer, and uses a material containing at least one metal element of tantalum or molybdenum as a heating element. By setting the heat generation temperature to 900 to 1600 ° C., a molded body that is colorless and transparent and has high gas barrier properties can be obtained.
(Chemical Formula 1) R ¹ R ² R ³ SiH
(In the general formula (Formula 1), R ¹ represents a methyl group, and R ² and R ³ represent hydrogen or a methyl group, or R ¹ represents a vinyl group, and R ² and R ³ Represents hydrogen or a methoxy group.)

  In the method for producing a gas barrier plastic molded body according to the present invention, the thickness of the adhesion layer is preferably 1 nm or more. The adhesion of the thin film can be further improved, and the development and stability of gas barrier properties can be further enhanced.

  In the method for producing a gas barrier plastic molded body according to the present invention, the gas barrier thin film further includes a protective layer on the gas barrier manifestation layer, and the heat barrier CVD method is formed on the gas barrier manifestation layer as the protective layer. It is preferable to have the step 3 of forming a layer in which one of the elements is Si after the step 2. By protecting the surface of the gas barrier developing layer, the stability of the gas barrier property can be further enhanced.

  In the method for producing a gas barrier plastic molded body according to the present invention, the thickness of the protective layer is preferably 3 nm or more. As described above, the stability of the gas barrier property of the plastic molded body can be enhanced. As a suitable example, a gas barrier thin film excellent in physicochemical stability (hereinafter referred to as water resistance in this specification) in an aqueous solution can be obtained. When the water resistance is insufficient, when the plastic molded body is a beverage container, the gas barrier property of the container gradually decreases after filling the beverage, which causes a problem in quality maintenance.

  In the method for producing a gas barrier plastic molded article according to the present invention, the plastic molded article includes a film, a sheet, or a container.

  The gas barrier plastic molding according to the present invention is formed by the method for producing a gas barrier plastic molding according to the present invention.

  INDUSTRIAL APPLICABILITY The present invention can provide a method for forming a gas barrier thin film having high gas barrier properties, transparency, and adhesiveness on the surface of a plastic molded body using a heating element CVD method.

It is the schematic which shows one form of the film-forming apparatus. It is sectional drawing which shows an example of the gas barrier plastic molding which concerns on this embodiment. It is sectional drawing which shows another example of the gas barrier plastic molding which concerns on this embodiment. It is a figure which shows the result of having performed the SIMS analysis regarding carbon and oxygen from the silicon substrate side to the adhesion layer side about the adhesion layer formed by the method of Example 4, or the adhesion layer formed by the plasma CVD method on the silicon substrate.

  Next, the present invention will be described in detail with reference to embodiments, but the present invention is not construed as being limited to these descriptions. As long as the effect of the present invention is exhibited, the embodiment may be variously modified.

  First, a film forming apparatus capable of forming a gas barrier thin film on the surface of a plastic molded body will be described. FIG. 1 is a schematic view showing an embodiment of a film forming apparatus. The film forming apparatus shown in FIG. 1 is an apparatus that can form a thin film on the inner surface of a container when the plastic molding is a container.

  The film forming apparatus 100 shown in FIG. 1 is inserted into and removed from 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, and the plastic container 11. A source gas supply pipe 23 formed of an insulating and heat-resistant material, which is arranged in a possible manner and supplies a source gas into the plastic container 11, a heating element 18 supported by the source gas supply pipe 23, and heat generation And a heater power supply 20 that energizes the body 18 to generate heat.

  The vacuum chamber 6 has a space for accommodating the plastic container 11 therein, and the space serves as 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 inside of the vacuum chamber 6, particularly the inside of the lower chamber 13, has an inner surface 28 that is a black inner wall or an inner surface that has a surface roughness (Rmax) in order to prevent reflection of light emitted as the heating element 18 generates heat. ) It is preferable to have irregularities 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 the cooling water flows inside or outside 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 because when the heating element 18 is inserted into the plastic container 11, the vacuum chamber 6 is in a state of being accommodated in the inner space of the lower chamber 13. By preventing light reflection and cooling the vacuum chamber 6, the temperature rise of the plastic container 11 and the accompanying thermal deformation can be suppressed. Furthermore, if a chamber 30 made of a transparent material through which the emitted light generated from the energized heating element 18 can pass, for example, a glass chamber, is disposed inside the lower chamber 13, the temperature of the glass chamber in contact with the plastic container 11 rises. Therefore, 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 raw material gas 33 or a carrier gas as required flows into the raw material gas supply pipe 23 via the flow rate regulators 24a, 24b, 24c or 24d and the valves 25a, 25b, 25c or 25d and 25e. When the material used as the source gas 33 is a liquid, the source gas 33 can be supplied by a bubbling method. That is, bubbling gas is supplied from the cylinder 42a, 42b or 42c to the starting raw material 41a, 41b or 41c accommodated in the raw material tank 40a, 40b or 40c while the flow rate is controlled by the flow rate regulator 24a, 24b or 24c. The vapor of the raw material 41a, 41b or 41c is generated and supplied as the raw material gas 33. The carrier gas is accommodated in the cylinder 42d and supplied while the flow rate is controlled by the flow rate regulator 24d. In the film forming apparatus shown in FIG. 1, when the material used as the source gas supplied through the valves 25a, 25b and 25c is a gas, the source gas is supplied to the cylinder 42a without providing the source tanks 40a, 40b or 40c. 42b or 42c, and the flow rate is controlled by the flow rate regulators 24a, 24b or 24c.

  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 source gas is blown out from the gas blowing hole 17x at the tip of the source 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 heating element 18 is energized and generates heat, the temperature of the source gas flow path 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 made 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 heating element can be stably energized, has durability, and can efficiently exhaust heat generated by the heating element by heat conduction.

  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 heating element is wired along the side wall of the source gas supply pipe, but the source gas that has passed through the hole provided in the side wall of the outer pipe contacts the heating element in the portion along the side wall to efficiently generate chemical species. Can be made.

  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. The uniformity of the film thickness is improved. A uniform thin 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, it may be difficult to form a thin film on the bottom of the plastic container 11. Further, if the distance is less than 5 mm, it may be difficult to blow out the source gas, or the film thickness distribution may be non-uniform. This fact can be grasped theoretically. In the case of a 500 ml container, since the container body diameter is 6.4 cm and the mean free path λ = 0.68 / Pa [cm] of air at room temperature, the molecular flow pressure <0.106 Pa and the viscous flow pressure> 10. 6 Pa, the intermediate flow is 0.106 Pa <pressure <10.6 Pa. At a gas pressure of 5 to 100 Pa during film formation, the gas flow changes from an intermediate flow to a viscous flow, and there is an optimum condition for the distance between the gas blowing hole 17x and the bottom of the plastic container 11.

  The heating element 18 promotes decomposition of the source gas in the heating element CVD method. In the present embodiment, the heating element 18 includes C, W, Ta, Ti, Hf, V, Cr, Mo, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt. It is preferable to be composed of a material containing one or two or more metal elements selected from the group. By having conductivity, it becomes possible to generate heat by energization. The heating element 18 is formed in a wiring shape, and is connected to one end of the heating element 18 at 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 point between the wiring 19 and the heating element 18. 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 heating element 18 is connected to the connecting portion 26b. As described above, since the heating element 18 is supported along the side surface of the source gas supply pipe 23, the heating element 18 is arranged so as to be positioned substantially on the main axis of the internal space of the lower chamber 13. Although FIG. 1 shows the case where the heating element 18 is arranged 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, the source gas supply pipe starts from the connection portion 26a. 23 may be spirally wound around the side surface of 23 and supported by the insulating ceramics 35 fixed in the vicinity of the gas blowing hole 17x, and then folded back toward the connecting portion 26b. Here, the heating element 18 is fixed to the source gas supply pipe 23 by being hooked on the insulating ceramic 35. FIG. 1 shows the case where the heating element 18 is disposed on the outlet side of the gas blowing hole 17x in the vicinity of the gas blowing hole 17x of the source gas supply pipe 23. As a result, the source gas blown out from the gas blowing holes 17x easily comes into contact with the heating element 18, so that the source gas can be activated efficiently. Here, it is preferable that the heating element 18 be disposed slightly away 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 source gas blown out from the gas blowing hole 17x and the source gas in the reaction chamber 12 can be increased. The outer diameter of the source gas supply pipe 23 including the heating element 18 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 heating element 18 is inserted from the mouth portion 21 of the plastic container. Therefore, if the heating element 18 is separated from the surface of the raw material gas supply pipe 23 more than necessary, it will be easy to contact when the raw material gas supply pipe 23 is inserted from the mouth portion 21 of the plastic container. The lateral width of the heating element 18 is suitably 10 mm or more and (inner diameter -6 of the mouth part -6) mm or less in consideration of positional displacement when inserted from the mouth part 21 of the plastic container. For example, the inner diameter of the mouth portion 21 is approximately 21.7 to 39.8 mm.

  The upper limit temperature when the heating element 18 is heated is preferably lower than the softening temperature of the heating element. Above the softening temperature, the heating element may be deformed and cannot be controlled. Although an upper limit temperature changes with materials of a heat generating body, for example, if it is molybdenum, 2300 degreeC is preferable. And if the heat generating body 18 is molybdenum, it is preferable that the temperature which operates the heat generating body 18 is 500-2200 degreeC, More preferably, it is 550-2000 degreeC, More preferably, it is 600-1200 degreeC. is there.

  The heating element 18 can generate heat by energization, for example. In the apparatus shown in FIG. 1, a heater power source 20 is connected to the heating element 18 via connection portions 26 a and 26 b and wiring 19. The heater 18 generates heat when electricity is supplied to the heater 18 by the heater power source 20. The present invention is not limited to the heating method of the heating element 18.

  Further, since the stretch ratio at the time of molding of the plastic container 11 is small from the mouth portion 21 of the plastic container to the shoulder of the container, if the heating element 18 that generates heat at a high temperature is disposed nearby, it is likely to be deformed by heat. According to the experiment, the shoulder portion of the plastic container 11 is thermally deformed unless the positions of the connection portions 26a and 26b, which are the connection points between the wiring 19 and the heating element 18, are 10 mm or more away from the lower end of the mouth portion 21 of the plastic container. When the thickness exceeded 50 mm, it was difficult to form a thin film on the shoulder portion of the plastic container 11. Therefore, the heating element 18 is preferably arranged so that the upper end thereof is located 10 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 connection portions 26a and 26b and the lower end of the mouth portion 21 is 10 to 50 mm. Thermal deformation of the shoulder portion of the container can be suppressed.

  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). .

  The film formation apparatus shown in FIG. 1 does not require a high-frequency power source, and the apparatus is cheaper than a plasma CVD apparatus. The apparatus for forming the gas barrier thin film 92 on the inner surface of the plastic container has been described. To form the gas barrier thin film 92 on the outer surface of the plastic container, for example, a film forming apparatus shown in FIG. It can be carried out. When the plastic molded body is a film or sheet, for example, the gas chamber thin film 92 is formed on the surface of the film or sheet by fixing the film or sheet along the inner wall of the reaction chamber 12 in a cylindrical shape. can do. Moreover, you may carry out the deformation | transformation which provides the winding apparatus which consists of the roll which rolls out the roll-shaped film or sheet in the vacuum chamber 6, and the roll which winds up the film or sheet in which the thin film was formed. Further, the film forming apparatus is not limited to the apparatus shown in FIG. 1, and various modifications can be made as shown in Patent Document 3, for example.

Next, the manufacturing method of the gas barrier plastic molding which concerns on this embodiment is demonstrated, referring FIG. FIG. 2 is a cross-sectional view showing an example of a gas barrier plastic molding according to the present embodiment. In the method for producing a gas barrier plastic molded body according to this embodiment, a gas barrier thin film 92 having an adhesion layer 81 and a gas barrier expression layer 82 sequentially on the surface of the plastic molded body 91 (in FIG. 1, the inner surface of the plastic container 11). In the manufacturing method of the gas barrier plastic molded body 90 that forms the organic silane compound represented by the general formula (Chemical Formula 1) as the raw material gas 33 on the surface of the plastic molded body 91 by the heating element CVD method, A step 1 of forming a layer in which one of the constituent elements is Si as the adhesion layer 81, and a step of forming a layer containing an oxide containing Al as the gas barrier development layer on the adhesion layer by the heating element CVD method. 2 and the step 2 uses dimethylaluminum isopropoxide as a source gas for forming the gas barrier expression layer, and Tantalum or a material containing at least one of the metal elements molybdenum used as the heat generator, the heat generation temperature of the heat generating body, and from 900 to 1,600 ° C..
(Chemical Formula 1) R ¹ R ² R ³ SiH
(In the general formula (Formula 1), R ¹ represents a methyl group, and R ² and R ³ represent hydrogen or a methyl group, or R ¹ represents a vinyl group, and R ² and R ³ Represents hydrogen or a methoxy group.)

  The method for producing a gas barrier plastic molded body includes a step of attaching the plastic molded body to the film forming apparatus, a step of adjusting the pressure in the reaction chamber, and a step of energizing the heating element before step 1. These will be described sequentially.

(Mounting plastic moldings on film deposition equipment)
First, a vent (not shown) is opened to open the vacuum chamber 6 to the atmosphere. In the reaction chamber 12, with the upper chamber 15 removed, a plastic container 11 as a plastic molded body 91 is inserted and accommodated from the upper opening of the lower chamber 13. Thereafter, the positioned upper chamber 15 is lowered, and the source gas supply pipe 23 attached to the upper chamber 15 and the heating element 18 fixed thereto are inserted into the plastic container 11 from the opening 21 of the plastic container. 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 distance between the inner wall surface of the plastic container 11 and the heating element 18 is also substantially uniform. It is kept in.

(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 preferably reduced until it reaches a required pressure, for example, 1.0 to 100 Pa. More preferably, it is 1.4-50 Pa. If it is less than 1.0 Pa, exhaust time may be required. Moreover, when it exceeds 100 Pa, impurities may increase in the plastic container 11 and high barrier properties may not be imparted. When the pressure is reduced to reach 1.4 to 50 Pa from atmospheric pressure, it is possible to obtain an appropriate residual water vapor pressure derived from the atmosphere, the device and the container together with an appropriate vacuum pressure, and easily an oxide thin film having a barrier property. Can be formed.

(Energization of heating element)
Next, the heating element 18 is caused to generate heat by energization, for example. The heating temperature of the heating element 18 is preferably 500 ° C. or higher. More preferably, it is 900 degreeC or more, More preferably, it is 1100 degreeC or more. The upper limit temperature of the heat generation temperature is preferably lower than the softening temperature of the heat generating element. Above the softening temperature, the heating element 18 may be deformed and cannot be controlled. Although an upper limit temperature changes with materials of the heat generating body 18, if it is molybdenum, 2300 degreeC is preferable, for example. More preferably, it is 2100 degreeC.

<Step 1: Adhesion layer forming step>
(Introduction of raw material gas for adhesion layer formation)
Thereafter, an organic silane compound represented by the general formula (Formula 1) is supplied as a source gas (hereinafter referred to as an adhesive layer forming source gas) 33 for forming the adhesion layer 81. In Formula 1, an organic silane compound in which R ¹ is a methyl group and R ² and R ³ are hydrogen or a methyl group includes, for example, monomethylsilane (CH ₃ SiH ₃ ), dimethylsilane ((CH ₃ ) ₂ SiH ₂ ) and trimethylsilane ((CH ₃ ) ₃ SiH). In Chemical Formula 1, the organic silane compound in which R ¹ is a vinyl group and R ² and R ³ are hydrogen or a methoxy group includes, for example, vinyl silane (CH ₂ CHSiH ₃ ), ethenyl (methoxy) silane (CH ₂ CHSiH ₂ (OCH ₃ )), dimethoxyvinylsilane (CH ₂ CHSiH (OCH ₃ ) ₂ ). Among these, dimethylsilane, vinylsilane, ethenyl (methoxy) silane, and dimethoxyvinylsilane are more preferable, and dimethylsilane, vinylsilane, and dimethoxyvinylsilane are particularly preferable. These can be used alone or in combination.

  The adhesion layer forming source gas 33 is supplied by controlling the flow rate with the gas flow rate regulator 24a. Further, the carrier gas is mixed with the adhesion layer forming raw material gas 33 before the valve 25e while the flow rate of the carrier gas is controlled by the gas flow rate regulator 24d as necessary. The carrier gas is an inert gas such as argon, helium or nitrogen. Then, the adhesion layer forming source gas 33 is supplied in the plastic container 11 whose pressure is reduced to a predetermined pressure in a state where the flow rate is controlled by the gas flow rate regulator 24a or in a state where the flow rate is controlled by the carrier gas. The gas is blown out from the gas blowing hole 17x of the gas supply pipe 23 toward the heating element 18 that has generated heat. Thus, it is preferable to start spraying the adhesion layer forming raw material gas 33 after the heating element 18 is heated. From the initial stage of film formation, the chemical species 34 sufficiently activated by the heating element 18 can be generated, and the adhesion to the plastic molded body can be further improved. The flow rate of the carrier gas is not particularly limited, but is preferably 0 to 80 sccm. In the present specification, the carrier gas flow rate of 0 sccm means that the source gas is supplied only by the vapor pressure of the liquid source without using the carrier gas. In this case, the gas flow rate regulator 24d is not normally used. . More preferably, it is 5-50 sccm. The pressure in the plastic container 11 can be adjusted to 10-30 Pa by the flow rate of the carrier gas.

  When the material used as the adhesion layer forming source gas 33 is a liquid, it can be supplied by a bubbling method. The bubbling gas used for the bubbling method is, for example, an inert gas such as nitrogen, argon, or helium, and nitrogen gas is more preferable. That is, when the starting material 41a in the material tank 40a is bubbled while controlling the flow rate with the gas flow regulator 24a using the bubbling gas filled in the cylinder 42a, the starting material 41a is vaporized and taken into the bubbles. Thus, the adhesion layer forming source gas 33 is supplied in a state of being mixed with the bubbling gas. Further, the carrier gas is mixed with the adhesion layer forming raw material gas 33 in front of the valve 25e while controlling the flow rate with the gas flow rate regulator 24d. Then, the adhesion layer forming source gas 33 is a heating element that generates heat from the gas blowing holes 17x of the source gas supply pipe 23 in the plastic container 11 whose pressure is reduced to a predetermined pressure while the flow rate is controlled by the carrier gas. It blows out toward 18. Here, the flow rate of the bubbling gas is preferably 0 to 50 sccm, and more preferably 0 to 50 sccm.

(Adhesion layer deposition)
When the adhesion layer forming source gas 33 comes into contact with the heating element 18, a chemical species 34 containing Si is generated. When the chemical species 34 reaches the inner wall of the plastic container 11, an adhesion layer 81 in which one of the constituent elements is Si is deposited. In the formation of the adhesion layer 81, the heating element 18 generates heat and the adhesion layer forming raw material gas 33 is sprayed onto the heating element 18 (hereinafter also referred to as film formation time) is 0.5 to 20 seconds. Is more preferable, and more preferably 1.0 to 8.5 seconds. The pressure in the vacuum chamber during film formation is preferably reduced until it reaches, for example, 1.0 to 100 Pa. More preferably, it is 1.4-50 Pa.

  In the heating element CVD method, the adhesion between the plastic container 11 and the thin film to be formed is very good. When hydrogen gas is introduced from the source gas channel 17, the hydrogen gas is activated by a catalytic decomposition reaction with the heating element 18, and the surface of the plastic container 11 can be cleaned by this active species. More specifically, a hydrogen abstraction reaction and etching action by activated hydrogen H * and hydrogen radical (atomic hydrogen) H can be expected, and these reactions and actions can be used for improving the adhesion of the thin film.

In addition, when NH ₃ gas is introduced from the raw material gas flow path 17, surface treatment for modifying and stabilizing the surface of the plastic container 11 can be performed by active species generated by catalytic decomposition reaction with the heating element 18. More specifically, addition of a nitrogen-containing functional group to the surface and a crosslinking reaction of a plastic polymer chain can be expected.

(Suspension of supply of adhesion layer forming source gas)
When the thin film reaches a predetermined thickness, the supply of the adhesion layer forming source gas 33 is stopped.

  In the method for producing a gas barrier plastic molded body according to the present embodiment, the thickness of the adhesion layer 81 is preferably 1 nm or more. More preferably, it is 2 nm, Especially preferably, it is 4 nm. If the film thickness of the adhesion layer 81 is less than 1 nm, a sufficient effect of forming the adhesion layer may not be obtained. The upper limit value of the adhesion layer 81 is not particularly limited, but is preferably 200 nm, more preferably 50 nm, and particularly preferably 10 nm from the viewpoint of economy and the prevention of cracking due to internal stress. Even if the thickness of the adhesion layer 81 exceeds 200 nm, there is no further effect and it is uneconomical.

<Process 2: Gas barrier expression layer formation process>
In the method for manufacturing a gas barrier plastic molded body according to the present embodiment, a layer containing an oxide containing at least one of Al, Si, and Ti as the gas barrier expression layer 82 on the adhesion layer 81 by the heating element CVD method. It is preferable to have step 2 of forming after step 1. Step 2 may be performed continuously after Step 1 without being released to the atmosphere or after Step 1 and once after being opened to the atmosphere and intermittently performed. It is preferable to carry out. Next, step 2 will be described in the case where it is performed continuously with step 1.

(Introduction of source gas for forming gas barrier layer)
After the supply of the adhesion layer forming raw material gas is stopped, a raw material gas 33 (hereinafter referred to as a gas barrier developing layer forming raw material gas) 33 for forming the gas barrier developing layer 82 is supplied. The gas barrier expression layer forming source gas 33 is a source material containing Al as a constituent element, a source material containing Si as a constituent element, or a raw material containing Ti as a constituent element among known source gases used in the CVD method. It is. These can be used alone or in combination.

  Raw materials containing Al as a constituent element include, for example, trialkylaluminum such as trimethylaluminum and triethylaluminum, aluminum halide such as aluminum chloride and aluminum bromide, tritertiary butoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, Metal aluminum alkoxides such as trisecondary butoxyaluminum, trisacetylacetonate aluminum, trisdipivaloylmethanate aluminum, dimethylaluminum isopropoxide (DMAIP), and trikis (trimethylsiloxy) aluminum. Among these, from the viewpoint of material cost and non-pyrophoric property (safety), metal aluminum alkoxide is more preferable, and DMAIP is particularly preferable.

  In the method for producing a gas barrier plastic molded body according to the present embodiment, step 2 uses DMAIP as the gas barrier layer forming source gas, and at least one of tantalum (Ta) and molybdenum (Mo) as the heating element 18. It is preferable that the heat generation temperature of the heating element 18 is set to 900 to 1600 ° C. using a material containing the metal element. A molded article that is colorless and transparent and has high gas barrier properties can be obtained.

  The raw material containing Si as a constituent element is, for example, a general formula (chemical formula 1) that can be used as a raw material gas for forming an adhesion layer such as monomethylsilane, dimethylsilane, trimethylsilane, vinylsilane, ethenyl (methoxy) silane, and dimethoxyvinylsilane. Organosilane compounds represented, dimethoxy (methyl) silane, ethoxydimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, tetramethoxysilane, tetramethylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethoxydimethylvinylsilane, allyltrimethyl Silane, diethoxydimethylsilane, tolylethylsilane, hexamethyldisiloxane, hexamethyldisilane, diethoxymethylvinylsilane, triethoxymethylsilane, triethoxyvinylsilane , Bis (trimethylsilyl) acetylene, tetraethoxysilane, trimethoxyphenylsilane, γ-glycidoxypropyl (dimethoxy) methylsilane, γ-glycidoxypropyl (trimethoxy) methylsilane, γ-methacryloxypropyl (dimethoxy) methylsilane, γ -Methacryloxypropyl (trimethoxy) silane, dihydroxydiphenylsilane, diphenylsilane, triethoxyphenylsilane, tetraisopropoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, tetra-n-butoxysilane, tetraphenoxysilane, poly (methylhydro) Gensiloxane), monoethylsilane, diethylsilane, triethylsilane, tetraethylsilane, dimethyldimethoxysilane.

  Examples of raw materials containing Ti as a constituent element include titanium halides such as titanium dichloride, titanium trichloride and titanium tetrachloride, tetraethoxytitanium, tetraisopropoxytitanium, tetranormalbutoxytitanium, tetrakisdimethylamidotitanium (TDMAT). And metal titanium alkoxides such as tetrakis (trimethylsiloxy) titanium. Among these, from the viewpoint of material cost and non-pyrophoric property (safety), metal titanium alkoxide is more preferable, and TDMAT is particularly preferable.

  The gas barrier expression layer forming raw material gas 33 is supplied while controlling the flow rate with a carrier gas as necessary, similarly to the raw material gas for forming the adhesion layer, except that the raw material gas 33 is supplied by controlling the flow rate with the gas flow regulator 24b. it can. Further, even when the gas barrier expression layer forming source gas 33 is a liquid, it is as described in the introduction of the adhesion layer forming source gas 33. Furthermore, it is preferable to mix an oxidizing gas into the gas barrier expression layer forming raw material gas 33. The oxidizing gas is, for example, oxygen, ozone, hydrogen peroxide, water vapor, nitrous acid gas, or carbon dioxide gas. The flow rate of the oxidizing gas is not particularly limited, but is preferably 0 to 80 sccm. More preferably, it is 5-50 sccm. Depending on the types of the gas barrier expression layer 92 and the raw material gas 33, degassing of the reaction chamber 12, residual gas components from the atmosphere, or degassing from the plastic molded body 11 can be used as the oxidizing gas.

(Deposition of gas barrier layer)
When the gas barrier expression layer forming source gas 33 comes into contact with the heating element 18, chemical species 34 derived from the gas barrier expression layer forming source gas are generated. When the chemical species 34 reaches the inner wall of the plastic container 11, a gas barrier expression layer 82 containing an oxide containing at least one of Al, Si, and Ti is deposited on the adhesion layer 81. . In the film formation of the gas barrier layer 82, the film formation time is preferably 1.0 to 20 seconds, and more preferably 1.0 to 8.5 seconds. The pressure in the vacuum chamber at the time of film formation is the same as that at the time of forming the adhesion layer.

(Stop supply of gas for gas barrier layer formation)
When the thin film reaches a predetermined thickness, the supply of the gas barrier developing layer forming raw material gas 33 is stopped. In the present embodiment, the thickness of the gas barrier expression layer 82 is not particularly limited, but in order to combine the gas barrier property expression effect, transparency, physicochemical stability such as adhesion and durability, The thickness is preferably 100 nm. More preferably, it is 10-50 nm.

(Finish film formation)
After exhausting the reaction chamber 12 again, a leak gas (not shown) is introduced to bring the reaction chamber 12 to atmospheric pressure. Thereafter, the upper chamber 15 is opened and the plastic container 11 is taken out. The thus obtained gas barrier plastic molded article can have a barrier property improvement rate (Barrier Improvement Factor, hereinafter referred to as BIF) of 5 or more, which is obtained by Equation 1. As a specific example, when the container capacity of the gas barrier plastic container is 2 liters or less, the oxygen permeability can be 0.0030 cc / container / day or less. In addition, the evaluation method of the film thickness of each layer which comprises the gas barrier thin film 92, and oxygen permeability is as having shown in the column of the Example.
(Equation 1) BIF = [Oxygen permeability of plastic molding without thin film] / [Oxygen permeability of gas barrier plastic molding]

<Step 3: Protective layer forming step>
FIG. 3 is a cross-sectional view showing another example of the gas barrier plastic molding according to the present embodiment. In the method for producing a gas barrier plastic molded body according to the present embodiment, the gas barrier thin film 92 further includes a protective layer 83 on the gas barrier developing layer 82, and the protective layer 83 is formed on the gas barrier developing layer 82 by a heating element CVD method. It is preferable to have Step 3 of forming a layer in which one of the constituent elements is Si after Step 2. Although step 3 can be performed continuously or intermittently with step 2, it is preferably performed continuously from the viewpoint of work efficiency. Specifically, the step 3 is preferably performed between the supply stop of the gas barrier expression layer forming source gas and the end of the film formation. Next, step 3 will be described in the case where it is performed continuously with step 2.

(Introduction of protective layer forming source gas)
After the supply of the gas barrier developing layer forming source gas is stopped, a source gas (hereinafter referred to as a protective layer forming source gas) 33 for forming the protective layer 83 is supplied. As the protective layer forming raw material gas 33, a raw material containing Si as a constituent element exemplified in the gas barrier expression layer forming raw material gas can be used. In particular, it is preferable to use an organosilane compound represented by the general formula (Formula 1) that can be used as a raw material gas for forming an adhesion layer. These can be used alone or in combination.

  The protective layer forming raw material gas 33 can be supplied while controlling the flow rate with a carrier gas as required, similarly to the adhesive layer forming raw material gas, except that the flow rate is controlled by the gas flow regulator 24c. . Further, the same material may be selected as the adhesion layer forming source gas and the protective layer forming source gas, and the cylinder 42a may also be used. Further, even when the gas barrier expression layer forming source gas 33 is a liquid, it is as described in the introduction of the adhesion layer forming source gas 33.

(Formation of protective layer)
When the protective layer forming source gas 33 comes into contact with the heating element 18, a chemical species 34 containing Si is generated. When the chemical species 34 reaches the inner wall of the plastic container 11, a protective layer 83 in which one of the constituent elements is Si is deposited on the gas barrier expression layer 82. In the formation of the protective layer 83, the film formation time is preferably 1.0 to 20 seconds, and more preferably 1.0 to 8.5 seconds. The pressure in the vacuum chamber at the time of film formation is the same as that at the time of forming the adhesion layer.

(Suspension of supply of protective layer forming source gas)
When the thin film reaches a predetermined thickness, the supply of the protective layer forming raw material gas 33 is stopped. In the method for producing a gas barrier plastic molded body according to the present embodiment, the thickness of the protective layer 83 is preferably 3 nm or more. More preferably, it is 4 nm, Especially preferably, it is 6 nm. If the thickness of the protective layer 83 is less than 3 nm, the effect of improving water resistance may be insufficient. The upper limit value of the protective layer 83 is not particularly limited, but is preferably 200 nm, more preferably 50 nm, and particularly preferably 10 nm from the viewpoints of economy and prevention of cracking due to internal stress. Even if the thickness of the protective layer 83 exceeds 200 nm, there is no effect of further improving the water resistance, which is uneconomical.

  In the method for producing a gas barrier plastic molded body according to this embodiment, it is preferable to further include a thermal annealing step. As the thermal annealing step, there is a method (referred to as Method 1) performed simultaneously with Step 3 or a method performed after Step 3 (referred to as Method 2). Method 1 is a method in which thermal annealing is performed simultaneously with the formation of the protective layer 83 while supplying the protective layer forming raw material gas 33. In Method 1, the heat generation temperature of the heating element 18 in Step 3 is set higher than the heat generation temperature in Step 1 or Step 2. In the thermal annealing step according to method 1, the heating temperature of the heating element 18 is preferably 1450 ° C. or higher, and more preferably 1950 ° C. or higher. If it is less than 1450 degreeC, the effect of a thermal annealing process may not be acquired. Moreover, it is preferable that the time which makes the heat generating body 18 generate | occur | produce heat is 1.0 to 5.0 second, More preferably, it is 1.5 to 2.0 second. Method 2 forms the protective layer 83 by forming the heat generation temperature of the heating element 18 at the same temperature as the heat generation temperature of step 1 or step 2, and when the thin film reaches a predetermined thickness, the protective layer forming raw material gas After the supply of 33 is stopped and the reaction chamber is evacuated for a certain period of time, the heating temperature of the heating element 18 is maintained at the same temperature as the heating temperature in step 1 or step 2. In the thermal annealing step according to method 2, the time during which the heating element 18 is heated is preferably 1.0 to 5.0 seconds, and more preferably 1.5 to 2.0 seconds. Through the thermal annealing process, the oxygen permeability of the gas barrier film can be further reduced. When the thermal annealing process is performed, energization to the heating element 18 is terminated after the thermal annealing process.

  Compared with other chemical vapor deposition methods such as plasma CVD or physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, ion plating, etc., the heating element CVD method is simpler and reduces the cost of the device itself. Can do. Further, in the heating element CVD method, since a gas barrier thin film is formed by deposition of chemical species, a dense film having a higher bulk density can be obtained as compared with the wet method.

  As shown in FIG. 2, the gas barrier plastic molded body 90 obtained through the steps 1 and 2 includes a gas barrier thin film 92 on the plastic molded body 91, and the gas barrier thin film 92 is formed on the plastic molded body 91. A close contact layer 81 and a gas barrier layer 82 formed on the close contact layer 81.

  Examples of the resin constituting the plastic molded body 91 include polyethylene terephthalate resin (PET), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin (PP), and 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 resin, polycarbonate resin, polysulfone resin, or tetrafluoroethylene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin . One of these may be used as a single layer, or two or more may be used as a laminate, but a single layer is preferable in terms of productivity. The type of resin is more preferably PET. Particularly noteworthy is that PET bottles are used in large quantities as beverage containers, while conventional heating element CVD methods are highly dangerous such as silane gas or trimethylaluminum and could not be practically used in beverage container manufacturing. On the other hand, the method of the present invention includes a method that is safe and can be carried out without difficulty in the production of beverage containers.

  The plastic molded body 91 is, for example, a container, a film, or a sheet. The shape can be appropriately set according to the purpose and application, and is not particularly limited. Examples of the container include 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 can be appropriately set 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. The present invention is not limited to the manufacturing method of the container. Examples of the contents include beverages such as water, tea beverages, soft drinks, carbonated beverages, and fruit juice beverages, liquids, viscous bodies, powders, and solid foods. Further, the container may be either a returnable container or a one-way container. The film or sheet includes a long sheet-like material and a cut sheet. It does not matter whether the film or sheet is stretched or unstretched. The present invention is not limited to the method for manufacturing the plastic molded body 91.

  The thickness of the plastic molded body 91 can be appropriately set according to the purpose and application, and is not particularly limited. When the plastic molded body 91 is a container such as a beverage bottle, for example, the thickness of the bottle is preferably 50 to 500 μm, and more preferably 100 to 350 μm. Moreover, when it is a film which comprises a packaging bag, it is preferable that the thickness of a film is 3-300 micrometers, More preferably, it is 10-100 micrometers. When the plastic molded body 91 is a substrate of a flat panel display such as electronic paper or organic EL, the thickness of the film is preferably 25 to 200 μm, and more preferably 50 to 100 μm. Moreover, when it is a sheet | seat for forming a container, it is preferable that the thickness of a sheet | seat is 50-500 micrometers, More preferably, it is 100-350 micrometers. When the plastic molded body 91 is a container, the gas barrier thin film 92 is provided on one 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 thin film 92 is provided on one side or both sides.

  By providing the adhesion layer 81, the adhesion between the plastic molded body 91 and the gas barrier thin film 92 is improved, and the gas barrier property is further improved. This effect is exhibited by using an organosilane compound represented by the general formula (Chemical Formula 1) as the adhesion layer raw material gas. The film thickness of the adhesion layer 81 is preferably 1 to 200 nm, more preferably 2 to 50 nm, and particularly preferably 4 to 10 nm in that the gas barrier property and / or water resistance can be further improved. The adhesion layer 81 contains Si and C as constituent elements. In addition to Si and C, the adhesion layer 81 may include a metal element derived from a heating element such as Mo (molybdenum), and other elements such as H (hydrogen), N (nitrogen), and O (oxygen). However, the oxygen element content of the adhesion layer 81 measured by X-ray photoelectron spectroscopy (XPS analysis) is preferably 0 to 60 at% (atomic%). More preferably, it is 0-55 at%, More preferably, it is 0-35 at% (atomic%). If the oxygen element content of the adhesion layer 81 exceeds 60 at%, the effect of improving the adhesion may be insufficient.

  The gas barrier expression layer 82 has a role of exhibiting high gas barrier properties. The gas barrier expression layer 82 preferably contains an oxide containing at least one of Al, Si, and Ti as a constituent element. Such an embodiment of the gas barrier expression layer 82 includes, for example, an embodiment containing aluminum oxide (AlOx), an embodiment containing silicon oxide (SiOx), an embodiment containing titanium oxide (TiOx), and AlOx and SiOx. Embodiments, embodiments containing AlOx and TiOx, embodiments containing SiOx and TiOx, embodiments containing a composite oxide of aluminum and silicon (AlSiOx), embodiments containing a composite oxide of aluminum and titanium (TiAlOx), Embodiment containing a composite oxide of silicon and titanium (TiSiOx), embodiment containing AlOx and AlSiOx, embodiment containing AlOx and TiAlOx, embodiment containing SiOx and AlSiOx, embodiment containing SiOx and TiSiOx , An embodiment containing TiOx and TiAlOx Embodiment containing a TiOx and TiSiOx, embodiments containing an AlOx and SiOx and TiOx, is an aspect that contains aluminum, a composite oxide of silicon and titanium (TiAlSiOx). The gas barrier expression layer 82 is not limited to the crystal type and the degree of oxidation of the oxide. The film thickness of the gas barrier layer 82 is preferably 5 to 200 nm. More preferably, it is 10-50 nm. The gas barrier expression layer 82 may contain other elements in addition to at least one of Al, Si, and Ti and an oxygen element. Other elements are, for example, metal elements derived from a heating element such as Mo (molybdenum), H (hydrogen), N (nitrogen), and C (carbon). However, the carbon element content of the gas barrier layer 82 measured by XPS analysis is preferably 0 to 30 at%. More preferably, it is 0-20 at%. When the content of the carbon element exceeds 30 at%, coloring is observed and the use may be limited.

  Further, through step 3, as shown in FIG. 3, a gas barrier plastic molded body 90 including a gas barrier thin film 92 further having a protective layer 83 on the gas barrier developing layer 82 can be obtained.

  The protective layer 83 has a role of protecting the surface of the gas barrier developing layer 82. The thickness of the protective layer 83 is preferably 3 to 200 nm. More preferably, it is 4-50 nm, Especially preferably, it is 6-10 nm. The protective layer 83 contains Si and C as constituent elements. In addition to Si and C, the protective layer 83 may include a metal element derived from a heating element such as Mo (molybdenum) and other elements such as H (hydrogen), N (nitrogen), and O (oxygen). However, the oxygen element content of the protective layer 83 measured by XPS analysis is preferably 0 to 60 at% (atomic%). More preferably, it is 0-55 at%, More preferably, it is 0-20 at% (atomic%). If the oxygen element content of the protective layer 83 exceeds 60 at%, the effect of improving water resistance may be insufficient.

  When an oxide thin film is directly formed on a plastic molded body, the oxide thin film is inferior in water resistance, so that there is a problem in that the thin film is cracked or peeled off in an aqueous solution and gas barrier properties cannot be maintained. In addition, an adhesion layer 81, an oxide thin film (gas barrier layer 82), and a protective layer 83 are sequentially provided on the plastic molding, and the film thickness of the adhesion layer is 2 nm or more and the film thickness of the protection layer is 3 nm or more. Thereby, water resistance can be improved and it can be set as the gas-barrier plastic molding suitable for the use which contacts water.

  According to the experiments conducted by the present inventors, a plastic container (hereinafter referred to as a gas barrier expression layer containing an oxide containing Al) directly formed on the inner surface of the container as an example of the gas barrier expression layer 82 directly on the plastic molded body 91. The BIF of the conventional container) was 7. On the other hand, a gas barrier plastic container in which an adhesion layer having a film thickness of 1 nm is formed on the inner surface of the container and a gas barrier expression layer containing an oxide containing Al is formed on the adhesion layer (hereinafter referred to as the present invention container A). ) Was 9.9, and the gas barrier property was improved. In this invention container A, in this invention container B which made the film thickness of the contact | adherence layer 4 nm or more, BIF became 25 and was able to further improve gas-barrier property. Further, when an aqueous solution of pH 4.0 or pH 6.8 was filled in a conventional container, damage such as cracks or peeling gradually occurred in the film, and the BIF decreased to less than 2.5. When water of pH 4.0 is filled in the container C of the present invention in which a protective layer having a thickness of 3 nm is formed on the expression layer, the film is not damaged and retains a high gas barrier property even after one month. It was confirmed that the gas barrier thin film had water resistance.

  Since the gas barrier plastic molded article according to the present embodiment has high gas barrier properties and transparency, it is suitable for packaging applications such as foods, medicines, pharmaceuticals, and electronic parts that are easily deteriorated by the influence of oxygen and the like. Furthermore, since it becomes a gas barrier thin film which has water resistance by making a contact | adherence layer and a protective layer more than predetermined film thickness, it is suitable as a packaging use for the food or drink containing water.

  Next, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited to the examples.

Example 1
As a plastic molded body, on the inner surface of a 500 ml PET bottle (height 133 mm, barrel outer diameter 64 mm, mouth outer diameter 24.9 mm, mouth inner diameter 21.4 mm, wall thickness 300 μm and resin amount 29 g), FIG. A gas barrier thin film was formed using the film forming apparatus shown. The pipes from the gas flow rate adjusters 24a to 24c to the gas supply port 16 were all made of 1/4 inch pipes made of stainless steel. The PET bottle was accommodated in the vacuum chamber 6 and decompressed until it reached 1.0 Pa. Next, two molybdenum wires having a diameter of φ0.5 mm and a length of 43 cm were used as the heating element 18, and a direct current of 8.2 V was applied to the heating element 18 to generate heat at 1100 ° C. Thereafter, dimethylsilane was supplied as an adhesion layer forming raw material gas from the gas flow controller 24a, and a layer having one of the constituent elements of Si as an adhesion layer was deposited on the inner surface of the PET bottle until the film thickness reached 2 nm. (Step 1). In the formation of the adhesion layer, the pressure during film formation was 4 Pa, and the film formation time was 2 seconds. Subsequently, DMAIP as a gas barrier development layer forming raw material gas and nitrogen gas as a carrier gas are supplied by a bubbling method from the gas flow regulator 24b, and a gas barrier development layer containing an oxide containing Al is formed on the adhesion layer. Was deposited until the thickness became 30 nm (step 2). In forming the gas barrier layer, the flow rate of the bubbling gas was 5 sccm, the pressure during film formation was 2.4 Pa, and the film formation time was 8.5 seconds. In this way, a gas barrier thin film having an adhesion layer and a gas barrier developing layer in order on the inner surface of the PET bottle was formed. The film thickness is a value measured using a stylus type step meter (model: α-step, manufactured by KLA-Eten).

(Example 2)
In Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 1 except that monomethylsilane was used instead of dimethylsilane as the raw material gas for forming the adhesion layer.

(Example 3)
In Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 1 except that trimethylsilane was used instead of dimethylsilane as the raw material gas for forming the adhesion layer.

(Example 4)
In Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 1 except that vinylsilane was used instead of dimethylsilane as the raw material gas for forming the adhesion layer.

(Example 5)
In Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 1 except that dimethoxyvinylsilane was used instead of dimethylsilane as the raw material gas for forming the adhesion layer.

(Example 6)
In Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 1 except that the thickness of the adhesion layer was 1 nm.

(Example 7)
In Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 1 except that the thickness of the adhesion layer was 4 nm.

(Example 8)
In Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 1 except that the thickness of the adhesion layer was 200 nm.

( Reference Example 9)
In Example 1, instead of dimethylaluminum isopropoxide, vinylsilane (30 sccm) is used as the gas barrier development layer forming raw material gas, and ozone (6 sccm) and oxygen (54 sccm) is used as the oxidizing gas. A gas barrier thin film was formed on the inner surface of the PET bottle in the same manner as in Example 1 except that a layer containing Si-containing oxide was deposited as a gas barrier developing layer on the adhesion layer.

( Reference Example 10)
In Example 1, instead of dimethylaluminum isopropoxide as the gas barrier development layer forming source gas, TDMAT was used, except that a layer containing an oxide containing Ti was deposited on the adhesion layer as a gas barrier development layer. In accordance with Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle.

(Example 11)
In Example 1, after forming the gas barrier manifestation layer, dimethylsilane is continuously supplied from the gas flow regulator 24c as a protective layer forming raw material gas, and one of the constituent elements as the protective layer is Si on the gas barrier manifestation layer. The layer was deposited until the film thickness was 4 nm (step 3). In forming the protective layer, the pressure during film formation was 4 Pa, and the film formation time was 4 seconds. Thus, a gas barrier thin film having an adhesion layer, a gas barrier expression layer, and a protective layer in order on the inner surface of the PET bottle was formed.

(Example 12)
In Example 11, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 11 except that the thickness of the protective layer was 200 nm.

(Example 13)
In Example 11, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 11 except that the thickness of the adhesion layer was 2 nm and the thickness of the protective layer was 3 nm.

(Example 14)
In Example 11, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 11 except that the thickness of the adhesion layer was 2 nm and the thickness of the protective layer was 2 nm.

(Example 15)
In Example 11, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 11 except that the thickness of the adhesion layer was 1 nm and the thickness of the protective layer was 4 nm.

(Example 16)
In Example 1, except that DMAIP and TDMAT are used as the gas barrier development layer forming source gas, and a layer containing an oxide containing Al and Ti is deposited on the adhesion layer as a gas barrier development layer. According to 1, a gas barrier thin film was formed on the inner surface of the PET bottle.

(Example 17)
In Example 1, except that DMAIP and vinylsilane were used as the gas barrier development layer forming raw material gas, and a layer containing an oxide containing Al and Si was deposited on the adhesion layer as a gas barrier development layer. According to 1, a gas barrier thin film was formed on the inner surface of the PET bottle.

(Comparative Example 1)
In Example 1, a gas barrier plastic molded article was obtained according to Example 1 except that phenylsilane (C ₆ H ₅ SiH ₃ ) was used instead of dimethylsilane as the adhesion layer forming raw material gas.

(Comparative Example 2)
In Example 1, the gas barrier plastic according to Example 1 except that hexamethyldisiloxane ((CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ ) was used instead of dimethylsilane as the raw material gas for forming the adhesion layer. A molded body was obtained.

(Comparative Example 3)
In Example 1, gas barrier plastic according to Example 1 except that hexamethyldisilazane ((CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ ) was used instead of dimethylsilane as the raw material gas for forming the adhesion layer. A molded body was obtained.

(Comparative Example 4)
In Example 1, a gas barrier plastic molded article was obtained according to Example 1 except that tetraethoxysilane (Si (OCH ₂ CH ₃ ) ₄ ) was used instead of dimethylsilane as the adhesion layer forming raw material gas. It was.

(Comparative Example 5)
In Example 1, a gas barrier plastic molded article was obtained according to Example 1 except that tetraethylsisilane (Si (CH ₂ CH ₃ ) ₄ ) was used instead of dimethylsilane as the adhesion layer forming raw material gas. It was.

(Comparative Example 6)
In Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 1 except that the adhesion layer was not formed and the gas barrier developing layer was formed directly on the inner surface of the PET bottle.

(Comparative Example 7)
In Reference Example 9, a gas barrier thin film was formed on the inner surface of the PET bottle according to Reference Example 9 except that the adhesion layer was not formed and the gas barrier expression layer was formed directly on the inner surface of the PET bottle.

(Comparative Example 8)
In Reference Example 10, a gas barrier thin film was formed on the inner surface of the PET bottle according to Reference Example 10 except that the adhesion layer was not formed and the gas barrier expression layer was formed directly on the inner surface of the PET bottle.

(Comparative Example 9)
In Example 16, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 16 except that the adhesion layer was not formed and the gas barrier developing layer was directly formed on the inner surface of the PET bottle.

(Comparative Example 10)
In Example 17, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 17, except that the adhesion layer was not formed and the gas barrier developing layer was formed directly on the inner surface of the PET bottle.

(Reference Example 1)
In Example 1, a gas barrier thin film was formed on the inner surface of the PET bottle according to Example 1 except that the gas barrier developing layer was not formed and only the adhesion layer was formed on the inner surface of the PET bottle.

(Reference Example 2)
In Example 1, instead of using dimethylsilane as the raw material gas for forming the adhesion layer, vinylsilane was used, and the gas barrier expression layer was not formed, but only the adhesion layer was formed on the inner surface of the PET bottle. According to 1, a gas barrier thin film was formed on the inner surface of the PET bottle.

  About the obtained plastic bottle provided with the gas barrier thin film of the Example and the comparative example, it evaluated by the following method.

  About the obtained plastic bottle provided with the gas barrier thin film of the Example and the comparative example, it evaluated by the following method.

(Adhesion evaluation)
By the methods described in Examples 1 to 8 and Comparative Examples 1 to 6, an adhesion layer and a gas barrier expression layer were sequentially formed on a 300 μm thick PET substrate. The film formation side of the obtained PET substrate sample was measured in a vacuum using an energy dispersive X-ray fluorescence spectrometer EDX-800HS manufactured by Shimadzu Corporation in a vacuum, measurement channel Al, 15 keV, 100 μA, capture range 0-20 keV , DT% 25, EDX analysis under the setting conditions of integration time 300 seconds, it was confirmed that all contain Al film components. Then, after immersing in distilled water at 30 ° C. for 3 weeks, rinsing with distilled water and drying, EDX analysis was performed again, and the signal strength of the obtained Al was less than 1/10 before immersion. The samples that had become non-adhesive, and the samples that had been held 1/10 or more were determined to have adhesiveness. By the method described in Reference Example 9, Example 17, Comparative Example 7 and Comparative Example 10, only the adhesion layer and the gas barrier expression layer were formed on a 300 μm thick PET substrate. In the EDX analysis on the film formation side of the obtained PET substrate sample, measurement and determination were performed by the same method as the analysis of the Al component except that the measurement channel Si was used. Further, only the adhesion layer and the gas barrier expression layer were formed on a 300 μm thick PET substrate by the method described in Reference Example 10, Example 16, Comparative Example 8 and Comparative Example 9. In the EDX analysis on the film formation side of the obtained PET substrate sample, measurement and determination were performed in the same manner as the analysis of the Al component except that the measurement channel Ti was used.

(BIF / gas barrier performance judgment)
In BIF, the oxygen permeability value of the PET bottle obtained in Example 1, Comparative Example, or Reference Example is defined as “Oxygen permeability of the gas barrier plastic molded body” in Equation 1, and the oxygen permeability of the PET bottle with no thin film formed. Was calculated as “oxygen permeability of a plastic molded body without a thin film”. The oxygen permeability was measured under the conditions of 23 ° C. and 90% RH using an oxygen permeability measuring device (model: Oxtran 2/20, manufactured by Modern Control), conditioned for 24 hours from the start of measurement, and then started measurement. The value after 72 hours had passed. The determination of the gas barrier performance is based on the change rate of the BIF of the example or the comparative example with respect to the reference value (the BIF / B of the example or comparative example) with respect to the reference value when the gas barrier expression layer is directly formed on the inner surface of the PET bottle. The following judgment criteria were used. The oxygen permeability of the PET bottle with no thin film formed was 0.0350 cc / container / day. BIF and determination results are shown in Table 1.
Gas barrier performance criteria:
○: BIF / reference value is 1.5 or more (there is an adhesion layer effect).
(Triangle | delta): BIF / reference value is 1.3 or more and less than 1.5 (the effect of an adhesion layer exists (lower limit)).
X: BIF / reference value is less than 1.3 (the effect of the adhesion layer is small (unsuitable)).
In the determination criteria, the reference value is BIF of Comparative Example 6 when the oxide element of the gas barrier developing layer is Al, and BIF of Comparative Example 7 when the oxide element of the gas barrier developing layer is Si. When the oxide element of the gas barrier developing layer is Ti, the BIF of Comparative Example 8 and when the oxide element of the gas barrier developing layer is Al and Ti, the BIF of Comparative Example 9 or the oxide of the gas barrier developing layer In the case where these elements are Al and Si, it is BIF of Comparative Example 10.

  As shown in Table 1, it was confirmed that the adhesion gas source gas used in Examples 1 to 17 has a practical level of adhesion effect of the gas barrier layer that is an oxide thin film. In addition, it was confirmed that by forming the adhesion layer using the organosilane compound represented by (Chemical Formula 1) as the source gas, the gas barrier property can be improved as compared with the case where the gas barrier expression layer is directly formed on the substrate. .

  On the other hand, in Comparative Examples 1 to 5, since an organic silane compound other than the organic silane compound represented by (Chemical Formula 1) was used as the adhesion layer forming raw material gas, a gas barrier expression layer was formed directly on the substrate. Compared with the case where it does, the effect which improves the adhesiveness of a gas barrier thin film was inadequate. Moreover, when the adhesion layer was formed using an organic silane compound other than the organic silane compound represented by (Chemical Formula 1), it was confirmed that there was no effect of improving the gas barrier property.

  Since Comparative Example 6 to Comparative Example 10 did not form the adhesion layer and the protective layer, the adhesion with the substrate was insufficient.

  From Reference Example 1 and Reference Example 2, it was confirmed that even if only the adhesion layer was formed, the gas barrier property was not expressed.

(With or without mixed layer)
In order to compare the adhesion layer of the present invention formed by the heating element CVD method and the adhesion layer formed by the plasma CVD method, the composition analysis of carbon and oxygen in the depth direction of the adhesion layer was performed by SIMS analysis. FIG. 4 shows the results of SIMS analysis on carbon and oxygen from the silicon substrate side to the adhesion layer side of the adhesion layer formed by the method of Example 4 or the adhesion layer formed by the plasma CVD method on the silicon substrate. FIG. Here, as the adhesion layer of the present invention, only the adhesion layer of Example 4 was formed on a silicon substrate, and SIMS analysis on carbon and oxygen was performed from the silicon substrate side to the adhesion layer side. On the other hand, the adhesion layer formed by the plasma CVD method is formed on the silicon substrate by the plasma CVD method disclosed in Japanese Patent Application Laid-Open No. 08-53116 using the raw material gas for the adhesion layer used in Example 4. An adhesion layer was formed under the conditions of a power output of 800 W, a source gas flow rate of 80 sccm, and a deposition time of 2 seconds, and SIMS analysis on carbon and oxygen was performed from the silicon substrate side to the adhesion layer side. The SIMS analysis was performed using PHI ADEPT-1010 manufactured by ULVAC-PHI. As measurement conditions, the primary ion species was set to Cs ⁺ , the primary acceleration voltage was set to 2.0 kV, and the detection region was set to 72 μm square.

  As shown in FIG. 4, the adhesion layer formed by the plasma CVD method is an element from the silicon substrate to the adhesion layer, particularly at the interface between the silicon substrate and the adhesion layer, as compared with the adhesion layer formed by the heating element CVD method according to Example 4. While the concentration change is gradual and carbon and oxygen ions enter the substrate side to form a mixed layer, the adhesion layer formed by the heating element CVD method is particularly at the interface between the silicon substrate and the adhesion layer. The result of supporting the expectation that the change in element concentration from the silicon substrate to the adhesion layer was steeper than that of the adhesion layer formed by the plasma CVD method and the mixed layer was not substantially formed was obtained.

  Next, evaluation which confirms water resistance was performed about the PET bottle of Examples 1-17 whose determination of BIF was a practical use level. The evaluation method is as follows.

(BIF change rate)
The plastic bottles of Examples 1 to 17 were filled with 490 ml of a phthalate pH standard solution (product number: 168-12145, manufactured by Wako Pure Chemical Industries, Ltd.) having a pH of 4.01 (25 ° C.) as a weakly acidic aqueous solution for one month. The sample was allowed to stand at an ambient temperature of 30 ° C. and used as a sample for water resistance (weak acidity) evaluation. Similarly, a phosphate pH standard solution (product number: 165-12155, manufactured by Wako Pure Chemical Industries, Ltd.) having a pH of 6.83 (25 ° C.) is used as a neutral aqueous solution for water resistance (neutral region) evaluation. A sample was used. BIF was determined for these samples. The BIF change rate is obtained from Equation 2 when the BIF before filling is BIF0 and the BIF of the water resistance evaluation sample is BIF1 (in Table 2, the weakly acidic aqueous solution is indicated as BIF1a and the neutral aqueous solution is indicated as BIF1n). It is a numerical value. The evaluation results are shown in Table 2.
(Expression 2) BIF change rate = BIF1 / BIF0

(Determination of water resistance)
The water resistance was determined as follows based on the value of BIF change rate. Table 2 shows the determination results.
Yes: BIF change rate is 0.5 or more.
None: BIF change rate is less than 0.5.

  As shown in Table 2, in Examples 1 to 10, Example 16, and Example 17, the protective layer was not formed, so water resistance was not obtained. In Example 14, since the protective layer was thin, water resistance was not obtained. In Example 15, since the film thickness of the adhesion layer was thin, water resistance was not obtained. Since Examples 11 to 13 had an adhesion layer and a protective layer, and the film thicknesses of the adhesion layer and the protective layer were sufficient, a gas barrier thin film having water resistance could be obtained.

  An additional test was conducted to examine the type of heating element and the heating temperature of the heating element suitable when DMAIP was used as the raw material gas for forming the gas barrier layer.

(Example 18)
In Example 4, an adhesion layer and a gas barrier expression layer were formed on the inner surface of the PET bottle in the same manner as in Example 4 except that the heating temperature of the heating element was changed to 900 ° C.

(Example 19)
In Example 4, an adhesion layer and a gas barrier expression layer were formed on the inner surface of the PET bottle in the same manner as in Example 4 except that the heating temperature of the heating element was changed to 1600 ° C.

(Example 20)
In Example 4, the heating element was changed to a tantalum wire instead of the molybdenum wire, and the adhesive layer and the inner surface of the PET bottle were changed in the same manner as in Example 4 except that the heating temperature of the heating element was changed to 900 ° C. A gas barrier developing layer was formed.

(Example 21)
In Example 20, an adhesion layer and a gas barrier expression layer were formed on the inner surface of the PET bottle in the same manner as in Example 20 except that the heat generation temperature of the heat generator was changed to 1600 ° C.

( Reference Example 22)
In Example 4, the heating element was changed to platinum-rhodium wire instead of molybdenum wire, and the exothermic temperature of the heating element was changed to 900 ° C. In the same manner as in Example 4, it adhered to the inner surface of the PET bottle. A layer and a gas barrier developing layer were formed.

( Reference Example 23)
In Reference Example 22, an adhesion layer and a gas barrier expression layer were formed on the inner surface of the PET bottle in the same manner as in Reference Example 22 except that the heating temperature of the heating element was changed to 1600 ° C.

(Example 24)
In Example 11, vinylsilane was used instead of dimethylsilane as the adhesion layer forming raw material gas, vinylsilane was used instead of dimethylsilane as the protective layer forming raw material gas, and the heating temperature of the heating element was changed to 900 ° C. Except for the above, an adhesion layer, a gas barrier expression layer, and a protective layer were sequentially formed on the inner surface of the PET bottle in the same manner as in Example 11.

(Example 25)
In Example 24, an adhesive layer, a gas barrier developing layer, and a protective layer were sequentially formed on the inner surface of the PET bottle in the same manner as in Example 24 except that the heat generation temperature of the heat generating element was changed to 1600 ° C.

(Example 26)
In Example 24, an adhesive layer, a gas barrier expression layer, and a protective layer were sequentially formed on the inner surface of the PET bottle in the same manner as in Example 24 except that the heating element was changed to a tantalum wire instead of the molybdenum wire.

(Example 27)
In Example 26, an adhesion layer, a gas barrier expression layer, and a protective layer were sequentially formed on the inner surface of the PET bottle in the same manner as in Example 26, except that the heating temperature of the heating element was changed to 1600 ° C.

( Reference Example 28)
In Example 24, an adhesive layer, a gas barrier expression layer, and a protective layer were sequentially formed on the inner surface of the PET bottle in the same manner as in Example 24 except that the heating element was changed to a platinum-rhodium wire instead of the molybdenum wire. .

( Reference Example 29)
In Reference Example 28, an adhesive layer, a gas barrier developing layer, and a protective layer were sequentially formed on the inner surface of the PET bottle in the same manner as in Reference Example 28 except that the heat generation temperature of the heating element was changed to 1600 ° C.

  The PET bottles of Examples 18 to 29 were evaluated for adhesion and BIF-gas barrier performance. The evaluation method is as described above. The results are shown in Table 3.

Example 18 and Example 19 is a case of using molybdenum as a heating element, Example 20 and Example 21 is the case using a tantalum heating element, also Reference Example 22 and Reference Example 23 In this case, an alloy of platinum and rhodium is used as the heating element. In any of the examples, by setting the heating temperature of the heating element in the range of 900 to 1600 ° C., the effect of having adhesion and improving the gas barrier property was obtained.

In Example 24 and Example 25, a protective layer was further provided on the gas barrier developing layer of Example 18 and Example 19, respectively, but the gas barrier properties were further improved. Similarly, in Example 26 and Example 27, a protective layer was further provided on the gas barrier expression layer of Example 20 and Example 21, respectively, but the gas barrier properties were further improved. Reference Example 28 and Reference Example 29 are obtained by further providing a protective layer on the gas barrier developing layer of Reference Example 22 and Reference Example 23, respectively, and further improving the gas barrier properties by providing the protective layer. Was not seen.

  Next, for the PET bottles of Examples 19, 21, 23, 25, 27, and 29, as an evaluation for confirming water resistance, the BIF change rate was obtained and water resistance was determined. The evaluation method is as described above. The results are shown in Table 4.

  In Examples 19, 21 and 23, the protective layer was not formed, so water resistance was not obtained. On the other hand, in Examples 25, 27 and 29, since a protective layer was formed, a gas barrier thin film having water resistance could be obtained.

  The gas barrier plastic molding according to the present invention is suitable as a packaging material. Moreover, the gas barrier container which consists of a gas barrier plastic molding which concerns on this invention is suitable as containers for drinks, such as water, a tea drink, a soft drink, a carbonated drink, and a fruit juice drink.

6 Vacuum chamber 8 Vacuum valve 11 Plastic container 12 Reaction chamber 13 Lower chamber 14 O-ring 15 Upper chamber 16 Gas supply port 17 Raw material gas flow path 17x Gas blowing hole 18 Heating element 19 Wiring 20 Heater power supply 21 Plastic container port 22 Exhaust Pipe 23 Source gas supply pipes 24a, 24b, 24c, 24d Flow rate regulators 25a, 25b, 25c, 25d, 25e Valves 26a, 26b Connection portion 27 Cooling water flow path 28 Inner surface 29 of vacuum chamber Cooling means 30 Chamber 33 made of a transparent body Raw material gas 34 Chemical species 35 Insulating ceramic member 40a, 40b, 40c Raw material tank 41a, 41b, 41c Starting material 42a, 42b, 42c, 42d Cylinder 81 Adhesion layer 82 Gas barrier expression layer 83 Protective layer 90 Gas barrier plastic molding 91 Plastic Molded body 92 gas barrier thin film 100 film forming apparatus

Claims (6)

In the method for producing a gas barrier plastic molded body, in which a gas barrier thin film having an adhesion layer and a gas barrier expression layer in order is formed on the surface of the plastic molded body,
On the surface of the plastic molded body, a layer in which one of the constituent elements is Si is formed as the adhesion layer using the organosilane compound represented by the general formula (Chemical Formula 1) as a source gas by the heating element CVD method. Step 1 to perform ,
Forming a layer containing an oxide containing Al as the gas barrier expression layer on the adhesion layer by a heating element CVD method; and
In the step 2, dimethylaluminum isopropoxide is used as a source gas for forming the gas barrier developing layer, and a material containing at least one metal element of tantalum or molybdenum is used as the heating element, and the heating element The method for producing a gas barrier plastic molding is characterized in that the exothermic temperature of the gas is 900 to 1600 ° C.
(Chemical Formula 1) R ¹ R ² R ³ SiH
(In the general formula (Formula 1), R ¹ represents a methyl group, and R ² and R ³ represent hydrogen or a methyl group, or R ¹ represents a vinyl group, and R ² and R ³ Represents hydrogen or a methoxy group.)   The method for producing a gas barrier plastic molding according to claim 1, wherein the thickness of the adhesion layer is 1 nm or more. The gas barrier thin film further has a protective layer on the gas barrier expression layer,
Wherein the gas barrier expression layer, with the heating element CVD method, the step 3 one of the configuration elements as the protective layer is to form a layer which is Si, to claim 1 or 2, characterized in that it has after the step 2 The manufacturing method of the gas barrier plastic molding as described. The method for producing a gas barrier plastic molding according to claim 3 , wherein the protective layer has a thickness of 3 nm or more. The method for producing a gas barrier plastic molded article according to any one of claims 1 to 4 , wherein the plastic molded article is a film, a sheet, or a container. A gas barrier plastic molded article formed by the method for producing a gas barrier plastic molded article according to any one of claims 1 to 5 .

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